CN117398993A

CN117398993A - High surface area PCC as catalyst support for platinum compounds

Info

Publication number: CN117398993A
Application number: CN202210778748.9A
Authority: CN
Inventors: J·弗托尼; A·杜塔乔杜里
Original assignee: Omya International AG
Current assignee: Omya International AG
Priority date: 2022-06-30
Filing date: 2022-06-30
Publication date: 2024-01-16

Abstract

The present invention relates to a catalytic processA system comprising a platinum compound on a solid support, wherein the content of platinum species on the surface of the solid support is from 0.1 to 15 wt% based on the dry weight of the solid support. The solid support is Precipitated Calcium Carbonate (PCC) and has a length of 15 to 100m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area/g; and the platinum compound is selected from elemental platinum, platinum oxides, and mixtures thereof. Furthermore, the invention relates to a process for preparing the catalytic system, to the use of the catalytic system according to the invention in chemical reactions, to the use of a solid support loaded with a platinum compound as catalyst, and to particles, mouldings or extrudates comprising the catalytic system.

Description

High surface area PCC as catalyst support for platinum compounds

Technical Field

The invention relates to a catalytic system comprising a platinum compound on a solid support, wherein the platinum compound is based on a solidThe dry weight of the carrier, the content of platinum species on the surface of the solid carrier is 0.1-15 wt.%. The solid support is Precipitated Calcium Carbonate (PCC) and has a length of 15 to 100m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area/g; and the platinum compound is selected from elemental platinum, platinum oxides, and mixtures thereof. Furthermore, the invention relates to a process for preparing the catalytic system, to the use of the catalytic system according to the invention in chemical reactions, to the use of a solid support loaded with a platinum compound as catalyst, and to a particulate moulding or extrudate comprising the catalytic system.

Background

Catalysts or catalytic systems comprising a support and a catalyst are widely used in catalysis and have several advantages. For example, the cost of handling such catalytic systems and separating the reaction products is lower than for homogeneous systems. Furthermore, the activity and efficiency of the catalytic system in a given reaction can be controlled by the choice of the particular structural properties of the support or of the particular platinum compound.

Platinum compounds are well known catalysts and can be used in many reactions, for example in the hydrogenation of olefins or alkynes. Known platinum compounds are, for example, elemental platinum.

Common support materials for heterogeneous catalysis are activated carbon, carbon black/graphite, alumina, barium sulfate and calcium carbonate (catalyst technical handbook (The Catalyst Technical Handbook), johnson Matthey company, 2005).

For example, DE2704345A1 relates to catalysts in the form of tablets, preforms or pellets, where the catalysts consist of CaCO ₃ 1 to 5 wt.% of platinum on a support.

WO2021/058508A1 relates to a catalytic system comprising a transition metal compound on a solid support, wherein the content of transition metal element on the surface of the solid support is from 0.1 to 30 wt% based on the dry weight of the solid support. The solid support may be calcium carbonate.

WO2004/030813A1 relates to a method for preparing a catalyst comprising (a) preparing a paste having a homogeneous mixture of at least one alkaline earth metal carbonate, a liquid medium, a silver bonding additive and at least one extrusion aid and/or optional burnout additive; (b) forming one or more shaped particles from the paste; (c) drying and calcining the particles; and (e) impregnating the dried and calcined particles with a solution containing a silver compound. The alkaline earth metal carbonate may be calcium carbonate.

WO2013/190076A1 relates to a catalytic system which is a Lindlar-type catalyst, wherein the support material (calcium carbonate) has an average particle size (d) ₅₀ ). It further discloses the use of such catalytic systems for the partial hydrogenation of carbon-carbon triple bonds to double bonds. Specific examples of carrier materials include precipitated calcium carbonate.

However, platinum compounds are only rare in natural resources and therefore, if possible, result in high costs for purchase and recycling. Another disadvantage is the toxicity of the platinum compounds, and therefore the catalyst loading in the platinum compound catalyzed reaction should be kept as low as possible. Accordingly, there is a continuing need for improved catalytic systems that overcome one or more of the above-described disadvantages.

Disclosure of Invention

It may therefore be an object of the present invention to provide a more efficient catalytic system which allows to reduce the catalyst loading and the total consumption of platinum compounds during catalysis and to obtain specific compounds, i.e. products with high selectivity. It may be another object of the present invention to provide a time-saving catalytic system with a higher conversion. Yet another object may be to provide a catalytic system that is easy to recycle to reduce the overall consumption of platinum compounds. Thus, another object may be to provide a more environmentally compatible catalytic system.

The foregoing and other problems may be solved by the subject matter as defined herein in the independent claims.

The first aspect of the present invention relates to a catalytic system comprising a platinum compound on a solid support, wherein

a) The solid support is Precipitated Calcium Carbonate (PCC) and has a length of 15 to 100m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area/g; and is also provided with

b) Wherein the platinum compound is selected from elemental platinum, platinum oxides, and mixtures thereof;

and wherein the content of the platinum species on the surface of the solid support is from 0.1 to 15% by weight based on the dry weight of the solid support.

The inventors of the present application have surprisingly found that there is 15-100m measured using nitrogen and the BET method according to ISO 9277:2010 ² The use of Precipitated Calcium Carbonate (PCC) of specific surface area per gram as a catalyst support in the catalysis of platinum compounds selected from the group consisting of elemental platinum, platinum oxides and mixtures thereof provides several advantages.

Firstly, the Precipitated Calcium Carbonate (PCC) used has a high surface area, i.e. 15 to 100m measured using nitrogen and the BET method according to ISO 9277:2010 ² Specific surface area per gram. Due to this high surface area, the material has been found to be surprisingly useful as a support material in catalysis.

In combination with, for example, the above-mentioned platinum compounds, higher catalytic activity, for example higher phenylacetylene conversion under hydrogen, is obtained using the catalytic system according to the invention. Furthermore, the catalytic system of the invention shows improved selectivity compared to commercially available platinum catalysts, in particular in alkyne hydrogenation, in particular under optimized reaction conditions and scale.

Another aspect of the invention relates to a method for preparing a catalytic system comprising a platinum compound on a solid support, said method comprising the steps of:

(a) Providing at least one solid support, wherein the solid support is Precipitated Calcium Carbonate (PCC) and has a thickness of 15 to 100m measured using nitrogen and BET method according to ISO 9277:2010 ² The specific surface area per gram of the polymer,

(b) Providing at least one platinum agent comprising Pt ions in an amount such that the amount of ions is from 0.1 wt% to 15 wt% based on the dry weight of the solid support,

(c) Contacting at least one solid support provided in step (a) with the platinum reagent provided in step (b) to obtain a mixture comprising the solid support and the platinum reagent; and

(d) Calcining the mixture of step (c) at a temperature of 200 ℃ to 600 ℃ to obtain a catalytic system comprising platinum oxide on a solid support.

The inventors have surprisingly found that by the above method, a catalytic system can be provided wherein the platinum compound on the solid support is a platinum oxide, wherein the solid support is Precipitated Calcium Carbonate (PCC) and has a thickness of 15 to 100m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area per gram. Furthermore, the above-described process is an inexpensive and simple preparation process which provides the catalytic system of the invention. Furthermore, the inventors have surprisingly found that by the above method, a catalytic system can be provided wherein the platinum compound is uniformly distributed on the surface of the high surface area Precipitated Calcium Carbonate (PCC).

Another aspect of the invention relates to the use of the catalytic system of the invention in a process comprising the steps of:

(A) Providing one or more reactants;

(B) Providing a catalytic system of the present invention;

(C) In the presence of the catalytic system provided in step (B), at a temperature of 50 to 300 ℃ at H ₂ Atmosphere or inert atmosphere and H ₂ Subjecting one or more reactants provided in step (a) to a chemical reaction in a liquid or gas phase under a combination of atmospheres.

Another aspect of the invention relates to the use of a solid support according to the invention, loaded with a platinum compound according to the invention, as a catalyst.

Finally, a further aspect of the invention relates to granules, mouldings or extrudates comprising the catalytic system of the invention.

It is to be understood that for the purposes of the present invention, the following terms have the following meanings:

within the meaning of the present invention, a "catalyst system" or "catalytic system" or "catalyst" is a system that increases the rate of a chemical reaction by adding such a substance/compound/system to the reactants (compounds converted during the reaction), wherein the substance/compound/system is not consumed in the catalytic reaction and can act continuously and repeatedly. In the presence of such a catalytic system, the chemical reaction occurs faster and/or with improved yields and/or improved selectivity, as it provides an alternative reaction pathway with lower activation energy than the non-catalytic mechanism.

In the meaning of the present invention, a "platinum reagent" is a reagent comprising platinum in ionic form. In the meaning of the present invention, a "platinum compound" is a compound comprising platinum in elemental form or as platinum oxide.

Within the meaning of the present invention, a "solid support" is understood to be a substance that can be loaded with a second substance (for example a platinum compound) in order to deliver said second substance to a target environment (for example a reactor) in order to easily restore the catalytic system at the end of the process and to allow a controlled size distribution of the metallic substance on the support surface during the preparation. In the present invention, the platinum compound is located on the surface of the precipitated calcium carbonate.

Within the meaning of the present invention, "ground natural calcium carbonate" (GNCC) is calcium carbonate obtained from natural sources, such as limestone, marble or chalk, and processed by wet and/or dry treatments, such as grinding, sieving and/or classification, for example by cyclone separators or classifiers.

Within the meaning of the present invention, "precipitated calcium carbonate" (PCC) is a synthetic material, typically obtained by precipitation after reaction of carbon dioxide and calcium hydroxide (slaked lime) in an aqueous environment or by precipitation of calcium and a carbonate source in water. In addition, the precipitated calcium carbonate may also be the product of the incorporation of calcium salts and carbonates, such as calcium chloride and sodium carbonate, in an aqueous environment. PCC may have a vaterite, calcite, or aragonite crystal form. PCC is described, for example, in EP 2 447213 A1, EP 2 524 898 A1, EP 2 371 766 A1, EP 2 840 065 A1 or WO 2013/142473 A1.

The "particle size" of the particulate material herein, such as precipitated calcium carbonate or particles of the catalytic system, is determined by its particle size distribution d _x (wt) to describe. Wherein the value d _x (wt) represents the diameter relative to which x wt% of the particles have a particle size less than d _x Diameter of (wt). This means, for example, d ₂₀ The (wt) value is 20% by weight of all particles of particles smaller than thisDegree. Thus d ₅₀ The (wt) value is the weight median particle size, i.e. 50 wt% of all particles are smaller than this particle size. By Sedigraph of U.S. Micromeritics Instrument Corporation ^TM 5120 a measurement is made. The methods and instruments are known to the skilled person and are generally used for determining particle size distribution. Measured at 0.1 wt% Na ₄ P ₂ O ₇ In aqueous solution. The dispersed sample was treated using a high speed stirrer and ultrasound.

Throughout this text, the "specific surface area" (in m ² The per gram meter) was determined using the BET method (using nitrogen as adsorption gas), which is well known to the person skilled in the art (ISO 9277:2010).

For the purposes of the present invention, the terms (cm) ³ "porosity" or "pore volume" of the meter/g) refers to the specific pore volume of the intra-particle intrusion. The porosity or pore volume is determined using the BJH method, which is well known to the skilled person (BS 4359-1:1996).

For the purposes of the present invention, "pore size" in terms of (nm or μm) refers to the intra-particle pore size. The pore size is determined using the BJH method, which is well known to those skilled in the art (BS 4359-1:1996).

Within the meaning of the present invention, a "suspension" or "slurry" comprises insoluble solids and a liquid medium, such as water, and optionally further additives, and generally contains a substantial amount of solids, and thus is more viscous and may have a higher density than the liquid from which it is formed.

The term "solid" according to the present invention refers to a material that is solid at Standard Ambient Temperature and Pressure (SATP), which refers to a temperature of 298.15K (25 ℃) and an absolute pressure of exactly 1 bar. The solid may be in the form of a powder, tablet, granule, flake, etc. Thus, the term "liquid medium" refers to a material that is liquid at Standard Ambient Temperature and Pressure (SATP), which refers to a temperature of 298.15K (25 ℃) and an absolute pressure of just 1 bar.

Where the term "comprising" is used in the present description and claims, it does not exclude other unspecified elements having a major or minor functional importance. For the purposes of the present invention, the term "consisting of … …" is considered to be a preferred embodiment of the term "comprising". If in the following a group is defined to contain at least a certain number of embodiments, this should also be understood as disclosing groups preferably consisting of only these embodiments.

Whenever the terms "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above.

When an indefinite or definite article is used when referring to a singular noun, e.g. "a", "an" or "the", this includes a plural of that noun unless something else is specifically stated.

Terms such as "obtainable" or "definable" and "obtained" or "defined" are used interchangeably. Unless the context clearly indicates otherwise, this for example means that the term "obtained" does not mean that for example an embodiment has to be obtained by for example the sequence of steps following the term "obtained" even if the term "obtained" or "defined" always includes such limited understanding as a preferred embodiment.

Advantageous embodiments of the catalytic system, the corresponding method of preparing the catalytic system and the use of the catalytic system according to the invention are defined in the following and the corresponding dependent claims.

In one embodiment according to the invention, the solid support has:

(i) Between 20 and 90m measured using nitrogen and BET method according to ISO 9277:2010 ² /g, preferably 25 to 80m ² /g, more preferably 30 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g; and/or

(ii) D in the range of 1 to 75 μm, preferably 2 to 50 μm, more preferably 3 to 40 μm, even more preferably 4 to 30 μm, most preferably 5 to 15 μm ₅₀ (wt); and/or

(iii) D in the range of 2 to 150 μm, preferably 4 to 100 μm, more preferably 6 to 80 μm, even more preferably 8 to 60 μm, most preferably 10 to 30 μm ₉₈ (wt)。

In another embodiment according to the invention, the platinum compound is selected from the group consisting of elemental platinum, ptO ₂ 、PtO ₃ And mixtures thereof, preferably selected from the group consisting of elemental platinum, ptO ₂ And mixtures thereof, most preferably elemental platinum.

According to another embodiment of the present invention, the content of platinum species on the surface of the solid support is in the range of 0.25 to 13 wt%, preferably 0.5 to 11 wt%, more preferably 1.0 to 10.0 wt%, even more preferably 1.5 to 8.0 wt%, most preferably 2.0 to 7.0 wt%, based on the dry weight of the solid support.

According to a further embodiment of the invention, the catalytic system is in particulate form and has:

(i) Between 15 and 80m measured using nitrogen and BET method according to ISO 9277:2010 ² /g, preferably 20 to 75m ² /g, more preferably 25 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g; and/or

(ii) D in the range of 1 to 75 μm, preferably 2 to 50 μm, more preferably 3 to 40 μm, even more preferably 4 to 30 μm, and most preferably 5 to 15 μm ₅₀ (wt); and/or

(iii) D in the range of 2 to 150 μm, preferably 4 to 100 μm, more preferably 6 to 80 μm, even more preferably 8 to 60 μm, and most preferably 10 to 30 μm ₉₈ (wt)。

According to yet another embodiment of the present invention, the method of the present invention further comprises step (e): at H ₂ Reducing the calcined catalytic system obtained from step (d) at a temperature of 100 ℃ to 500 ℃ under an atmosphere to obtain a catalytic system comprising elemental platinum, platinum oxides and mixtures thereof.

According to yet another embodiment of the present invention, the calcination step (d) is performed under the following conditions:

(i) In the air, N ₂ Atmosphere, ar atmosphere, O ₂ Under an atmosphere or mixture thereof, and/or

(ii) At a temperature of 270 ℃ to 480 ℃, preferably at a temperature of 300 ℃ to 450 ℃, most preferably at a temperature of 330 ℃ to 400 ℃.

According to yet another embodiment of the invention, the method of the invention further comprises step (f): providing a solvent and contacting the at least one solid support provided in step (a) and/or the platinum reagent provided in step (b) in any order before or during step (c), and preferably the solvent is a non-polar solvent, a polar solvent or a mixture thereof, more preferably the non-polar solvent is selected from pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane and a mixture thereof, and/or the polar solvent is selected from tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and a mixture thereof, even more preferably the solvent is a polar solvent, most preferably the solvent is water.

According to yet another embodiment of the invention, the method of the invention further comprises step (g): removing at least part of the solvent by evaporation and/or filtration and/or centrifugation and/or spray drying after step (c) and before step (d) to obtain a concentrated mixture.

According to yet another embodiment of the invention, the method of the invention further comprises step (h): heat treating the mixture of step (c) or the concentrated mixture of step (g) at a temperature of 25 ℃ to 200 ℃, preferably at a temperature of 50 ℃ to 180 ℃, most preferably at a temperature of 100 ℃ to 150 ℃.

According to another embodiment of the invention, the platinum agent is selected from KPt (NH) ₃ )Cl ₃ 、Pt(NH ₃ ) ₂ Cl ₂ 、K[(H ₂ C＝CH ₂ )PtCl ₃ ]·xH ₂ O、Na ₂ PtCl ₆ 、Pt(acac) ₂ 、Na ₂ PtCl ₄ 、H ₂ PtCl ₆ 、(NH ₄ ) ₂ [PtCl ₆ ]、PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof, preferably selected from Na ₂ PtCl ₆ 、Pt(acac) ₂ 、Na ₂ PtCl ₄ 、H ₂ PtCl ₆ 、(NH ₄ ) ₂ [PtCl ₆ ]、PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof, most preferably selected from PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof.

According to another embodiment of the invention, the method of the invention further comprises step (D): recovering and optionally recycling the catalytic system after the chemical reaction of step (C).

According to another embodiment of the invention, the chemical reaction in step (C) is selected from one or more of alkene hydrogenation and alkyne hydrogenation, and preferably from one or more of alkyne hydrogenation.

Process for the preparation of a catalytic system

As described above, the method of preparing the catalytic system of the present invention comprising a platinum compound on a solid support comprises steps (a) - (d). The method optionally further comprises steps (e) and/or (f) and/or (g) and/or (h).

It will be appreciated that the process of the present invention, i.e. the process for preparing the catalytic system of the present invention, may be carried out as a continuous process or as a batch process. Preferably, the process of the present invention is carried out as a batch process.

Reference will now be made in further detail to the present invention, particularly to the foregoing steps of the method of the present invention, for locating platinum compounds on the surface of precipitated calcium carbonate having a high specific surface area.

It is to be understood that the defined embodiments of the process of the invention are also applicable to the catalytic system of the invention, as well as to the use of the catalytic system of the invention, the use of a solid support carrying a platinum compound as catalyst, and differently shaped products of the invention such as granules, molded articles or extrudates, and vice versa.

Step (a): providing at least one solid support

According to the invention, in step (a) at least one solid support is provided, wherein the solid support is Precipitated Calcium Carbonate (PCC) having a thickness of 15 to 100m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area per gram.

The expression "at least one" solid support means that one or more, for example, two or three, solid supports may be provided. According to a preferred embodiment, the at least one solid support comprises only one solid support as provided in step a).

Within the meaning of the present invention, "precipitated calcium carbonate" (PCC) is a synthetic material, typically obtained by precipitation after reaction of carbon dioxide and lime in an aqueous environment, or by precipitation of calcium and a source of carbonate ions in water, or by combining calcium and carbonate ions (e.g. CaCl ₂ And Na (Na) ₂ CO ₃ ) And is precipitated from solution. Other possible ways to prepare PCC are lime soda processes, or Solvay processes where PCC is a byproduct of ammonia production.

Precipitated calcium carbonate exists in three main crystalline forms: calcite, aragonite and vaterite, and each of these crystal forms has many different polymorphs (crystal habits). Calcite has a triangular structure, typical crystal habit such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, axillar, colloidal (C-PCC), cubic and prismatic (P-PCC). Aragonite is an orthorhombic structure, the typical crystal habit of which is a double hexagonal prismatic crystal, and a variety of fine elongated prisms, curved blades, steep pyramids, chisel crystals, branching tree and coral or worm-like forms. Vaterite belongs to the hexagonal system. The PCC slurry obtained may be washed, mechanically dewatered and dried by known methods, for example by flocculation, filtration or forced evaporation prior to drying. The subsequent drying step (if desired) may be carried out in a single step, such as spray drying, or in at least two steps.

For the purposes of step (a) of the present invention, the solid support may be provided in dry form or as a suspension in a suitable liquid medium. Unless otherwise indicated, the term "dried" or "dried" refers to a material having a constant weight at 200 ℃, where constant weight refers to a change of 1mg or less per 5g of sample over a period of 30 seconds.

According to one embodiment, the solid support is provided in the form of a slurry in a solvent. According to one embodiment, the solvent is a non-polar solvent, a polar solvent or a mixture thereof, more preferably the non-polar solvent is selected from pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane and mixtures thereof, and/or the polar solvent is selected from tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and mixtures thereof, even more preferably the solvent is a polar solvent, and most preferably the solvent is water. According to one embodiment of the invention, the slurry comprising precipitated calcium carbonate has a precipitated calcium carbonate content of from 1 to 90 wt. -%, more preferably from 3 to 60 wt. -%, even more preferably from 5 to 40 wt. -%, and most preferably from 10 to 25 wt. -%, based on the total weight of the slurry. The precipitated calcium carbonate slurry may optionally be further stabilized by a dispersant. Conventional dispersants known to those skilled in the art may be used. Preferred dispersants consist of polyacrylic acid and/or carboxymethylcellulose.

Alternatively, the resulting PCC slurry may be dried as described above, thereby obtaining precipitated calcium carbonate as a solid in particulate or powder form (i.e., dried or containing as little water as possible in a non-fluid form).

In a preferred embodiment, the solid support is provided in dry form.

According to one embodiment of the invention, the at least one solid carrier is precipitated calcium carbonate, preferably comprising an aragonite, vaterite or calcite mineralogical crystal form or a mixture thereof.

According to one embodiment of the invention, the at least one solid support comprises a type of precipitated calcium carbonate. According to another embodiment of the invention, the at least one solid carrier comprises a mixture of two or more precipitated calcium carbonates selected from different crystalline forms and different polymorphs of precipitated calcium carbonate. For example, the at least one precipitated calcium carbonate may comprise one PCC selected from S-PCC and one PCC selected from R-PCC.

It will be appreciated that the amount of calcium carbonate in the at least one solid support is at least 80 wt%, such as at least 95 wt%, preferably 97 wt% to 100 wt%, more preferably 98.5 wt% to 99.95 wt%, based on the total dry weight of the at least one solid support.

The at least one solid support is preferably in the form of a particulate material and may have a particle size distribution conventionally used with the material(s) involved in the type of product to be prepared. In general, a weight median particle size d of the at least one solid support is preferred ₅₀ The values are in the range of 1 to 75 μm. For example, the at least one solid support has a weight median particle size d ₅₀ From 2 μm to 50 μm, more preferably from 3 to 40 μm, even more preferably from 4 to 30 μm, and most preferably from 5 μm to 15 μm.

Additionally or alternatively, the at least one solid support has a top cut (d) of 2 to 150 μm, preferably 6 to 80 μm, even more preferably 8 to 60 μm, and most preferably 10 to 30 μm ₉₈ )。

The at least one solid support has a size of 15 to 100m as measured by BET nitrogen method ² BET specific surface area per gram. According to a preferred embodiment, the at least one solid support has a BET nitrogen method according to ISO 9277:2010 of 20 to 90m ² /g, more preferably 25 to 80m ² /g, more preferably 30 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area per gram (BET).

Additionally or alternatively, the at least one solid support has a residual total moisture content of from 0.01 to 1 wt%, preferably from 0.01 to 0.2 wt%, more preferably from 0.02 to 0.2 wt% and most preferably from 0.03 to 0.2 wt%, based on the total dry weight of the at least one solid support.

Thus, it is preferred that the at least one solid support has:

(i) Between 15 and 100m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area in the range of/g; and one or more of the following features:

According to a preferred embodiment, the at least one solid support has:

Alternatively, the at least one solid support has:

(i) Between 20 and 90m measured using nitrogen and BET method according to ISO 9277:2010 ² /g, preferably 25 to 80m ² /g, more preferably 30 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g; and

(ii) D in the range of 1 to 75 μm, preferably 2 to 50 μm, more preferably 3 to 40 μm, even more preferably 4 to 30 μm, and most preferably 5 to 15 μm ₅₀ (wt); and

According to a preferred embodiment of the invention, the at least one solid support is Precipitated Calcium Carbonate (PCC) and has

(i) 30 to 70m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area per gram, and

According to another embodiment, the precipitated calcium carbonate has a length of 0.001 to 2.3cm measured using the BJH method according to BS 4359-1:1996 ³ /g, more preferably 0.01 to 1.5cm ³ Preferably 0.02 to 1.0cm ³ /g, most preferably 0.02 to 0.5cm ³ Specific pore volume of intraparticle intrusion per gram.

The particle diameter of the precipitated calcium carbonate, measured using the BJH method according to BS 4359-1:1996, is preferably from 0.004 to 1.6. Mu.m, more preferably from 0.005 to 1.0. Mu.m, particularly preferably from 0.006 to 0.80. Mu.m, and most preferably from 0.007 to 0.50. Mu.m, for example from 0.010 to 0.10. Mu.m.

Step (b): providing at least one platinum reagent

In step (b) of the preparation method according to the invention, at least one platinum reagent is provided.

The expression "at least one" platinum agent means that one or more, for example two or three platinum agents may be provided. According to a preferred embodiment, the at least one platinum agent comprises only one solid support as provided in step b).

The platinum agent according to the present invention comprises Pt ions and mixtures thereof and is provided in such an amount that the amount of the ions is 0.1 to 15 wt% based on the dry weight of the solid support.

In principle, there are four types of reagents, depending on how the constituent atoms are bound together: molecules bound together by covalent bonds, salts bound together by ionic bonds, intermetallic compounds bound together by metallic bonds, and certain complexes bound together by coordinate covalent bonds. Thus, the platinum reagent may be a molecular platinum reagent, a platinum salt, a platinum compound comprising an elemental platinum compound, or a platinum complex.

According to a preferred embodiment of the invention, the platinum agent is a platinum salt or a platinum complex.

In another preferred embodiment according to the invention, the platinum reagent comprises one or more of the following counter ions: hydrogen ion, sulfide ion, fluoride ion, chloride ion, bromide ion, iodide ion, carbonate, acetate, cyanide, thiocyanate, nitrate, nitrosylnitrate, phosphate, and sulfate.

In another preferred embodiment, the platinum agent comprises one or more of the following ligands: acetylacetone (acac), chloride, acetate, triphenylphosphine, 1' -bis (diphenylphosphino) ferrocene (dppf), 1, 2-bis (diphenylphosphino) ethane (dppe), 1, 3-bis (diphenylphosphino) propane (dppp), 1, 4-bis (diphenylphosphino) butane (dppb), allyl, dibenzylideneacetone or dibenzylideneacetone (dba), and ethylenediamine.

According to a preferred embodiment, the platinum salt and/or the platinum complex is water-soluble, thus forming a solution when dissolved in water. The "absolute water solubility" of a compound is understood to be the maximum concentration of the compound in water, wherein a single phase mixture can be observed under equilibrium conditions at 20 ℃. Absolute water solubility is given in grams of compound per 100 grams of water. According to a preferred embodiment, the platinum salt and/or the platinum complex has an absolute water solubility of more than 0.1g/100g water, preferably more than 1g/100g water, and most preferably more than 5g/100g water.

According to another embodiment of the invention, the platinum agent is selected from KPt (NH) ₃ )Cl ₃ 、Pt(NH ₃ ) ₂ Cl ₂ 、K[(H ₂ C＝CH ₂ )PtCl ₃ ]·xH ₂ O、Na ₂ PtCl ₆ 、Pt(acac) ₂ 、Na ₂ PtCl ₄ 、H ₂ PtCl ₆ 、(NH ₄ ) ₂ [PtCl ₆ ]、PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof, preferably selected from Na ₂ PtCl ₆ 、Pt(acac) ₂ 、Na ₂ PtCl ₄ 、H ₂ PtCl ₆ 、(NH ₄ ) ₂ [PtCl ₆ ]、PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof, most preferably selected from PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof. These compounds are known to those skilled in the art and are commercially available.

For the purpose of step (b), the platinum reagent may in principle be provided in any form, which means that the platinum reagent may be provided as a pure compound, or it may be provided in a liquid medium in the form of a solution or suspension.

The platinum agent according to the invention is provided in such an amount that the amount of ions is 0.1 to 15 wt.% based on the dry weight of the solid support. Alternatively, the platinum agent according to the present invention is provided in such an amount that the amount of ions is 0.25 to 13 wt%, preferably 0.5 to 11 wt%, more preferably 1.0 to 10.0 wt%, even more preferably 1.5 to 8.0 wt%, and most preferably 2.0 to 7.0 wt%, based on the dry weight of the solid support.

Optional step (f): providing a solvent

According to one embodiment of the invention, the method further comprises an optional step (f): providing a solvent and contacting the at least one solid support provided in step (a) and/or the platinum reagent provided in step (b) in any order before or during step (c).

According to one embodiment of the present invention, only the at least one solid support provided in step (a) is contacted with a solvent. The solids content of the slurry may be from 1 to 95 wt%, preferably from 3 to 60 wt%, more preferably from 5 to 40 wt%, and most preferably from 10 to 25 wt%, based on the total weight of the slurry. At least one platinum agent is added to the slurry obtained in dry form.

Alternatively, contacting the at least one platinum reagent provided in step (b) with a solvent. The solids content of the slurry or solution may be from 0.1 to 50 wt%, preferably from 0.1 to 40 wt%, more preferably from 0.2 to 3 wt%, and most preferably from 0.5 to 10 wt%, based on the total weight of the slurry or solution. Adding at least one solid support in dry form to the slurry or solution obtained.

In step (f), it may be preferred to contact the at least one platinum reagent provided in step (b) with a solvent, as this may result in a more homogeneous mixture in any subsequent step, for example in contact step (c) of the process of the invention for preparing a catalytic system. For the same reasons, solutions may be more preferred than suspensions. Thus, in a preferred embodiment, the platinum agent provided in step (b) is in the form of a solution or suspension, preferably in the form of a solution, in step (c).

According to a preferred embodiment, two solvents are provided. Contacting the at least one solid support provided in step (a) with one solvent and the at least one platinum reagent provided in step (b) with another solvent. The two slurries or slurry and solution are then mixed.

The solvent used to provide the at least one solid support and the solvent used to provide the at least one platinum agent may be the same or different. According to a preferred embodiment, the two solvents are identical.

According to one embodiment, the solvent is a non-polar solvent, a polar solvent or a mixture thereof.

According to a preferred embodiment of the present invention, the non-polar solvent is selected from the group consisting of pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane and mixtures thereof. According to another preferred embodiment of the present invention, the polar solvent is selected from tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and mixtures thereof.

According to another preferred embodiment of the invention, the solvent for the solid support and/or the platinum agent is a polar solvent, most preferably water.

Step (c): contacting at least one solid support with a platinum reagent

In step (c) of the preparation process according to the invention, the at least one solid support provided in step (a) is contacted with the at least one platinum reagent provided in step (b), resulting in a mixture comprising the solid support and the platinum reagent.

Step (c) of contacting the solid support with a platinum reagent serves to impregnate at least a portion of the accessible surface of the solid support with the platinum reagent.

The contacting of the at least one solid support provided in step (a) with the at least one platinum reagent provided in step (b) may be accomplished by any conventional method known to those skilled in the art.

According to one embodiment of the invention, step (c) comprises the steps of: providing in a first step the at least one solid support provided in step (a) and then adding in a subsequent step the at least one platinum reagent provided in step (b). According to another embodiment of the invention, step (c) comprises the steps of: first providing the at least one platinum reagent provided in step (b), followed by adding the at least one solid support provided in step (a). According to another embodiment, the at least one solid support provided in step (a) and the at least one platinum agent provided in step (b) are provided and contacted simultaneously.

In the case where the at least one solid support provided in step (a) is provided as a first step, the at least one platinum agent provided in step (b) may be added in one portion, or may be added in several equal or unequal portions, i.e. in larger and smaller portions.

During the contacting step (c) of the process of the present invention, a mixture is obtained comprising the solid support of step (a) and the platinum reagent of step (b). The mixture may be a solid, preferably in powder form, or a suspension or slurry in liquid form. Preferably, the mixture is a suspension or slurry in liquid form.

In one embodiment of the process according to the invention, (i) the at least one solid support of step (a) is provided in the form of a suspension in a solvent; and/or (ii) at least one platinum agent of step (b) is provided in the solvent in the form of a solution or suspension, preferably in the form of a solution.

In a preferred embodiment, the solid support is provided in the form of a suspension in a solvent, wherein the platinum agent is also provided in the form of a solution or suspension, preferably in the form of a solution in a solvent.

As already described above, the solid support may be provided as a suspension or slurry, in which case the suspension or slurry will contain a suitable solvent. In general, the solvent may be different from the solvents described herein as a suitable solvent for providing at least one platinum agent in solution or suspension.

However, in a preferred embodiment, the solvent used to provide the at least one solid support and the solvent used to provide the at least one platinum agent are the same.

The mixture obtained in step (c) may comprise any of the solvents disclosed above, for example the solvent may be a non-polar solvent, a polar solvent or a mixture thereof, preferably the non-polar solvent is selected from pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane and mixtures thereof, and/or the polar solvent is selected from tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and mixtures thereof. Preferably, the mixture obtained in step (c) further comprises water, ethanol/water mixtures, toluene and mixtures thereof, most preferably further comprises water.

The contacting step (c) may be performed by any method known in the art. For example, the at least one solid support of step (a) and the platinum reagent of step (b) may be contacted by spraying and/or mixing. Suitable means for spraying or mixing are known to the person skilled in the art.

According to one embodiment of the invention, step (c) may be performed by spraying. Preferably, step (c) is performed by mixing.

The mixing in step (c) may be accomplished by any conventional method known to those skilled in the art. The skilled person will adjust the mixing conditions, such as mixing speed, segmentation and temperature, according to his process equipment. In addition, the mixing may be performed under homogenization and/or particle segmentation (differentiation) conditions.

For example, mixing and homogenization may be performed by using a ploughshare mixer. The ploughshare mixer works by the mechanically generated fluid bed principle. The ploughshare blades rotate close to the inner wall of the horizontal cylindrical drum, transporting the components of the mixture out of the product bed and into the open mixing space. The fluidized bed ensures intensive mixing of even large batches in a very short time. In the case of a dry mode of operation, a shredder and/or a disperser is used to disperse the agglomerates. The apparatus which can be used in the process of the invention is commercially available, for example, from Gebru cathedige machinenbau GmbH, germany or from VISCO JET Huhrsystem GmbH, germany.

According to another embodiment of the invention, step (c) is performed for at least 1 second, preferably at least 1 minute (e.g. 10 minutes, 30 minutes or 60 minutes). According to a preferred embodiment, step (c) is carried out for a period of 1 second to 60 minutes, preferably for a period of 15 minutes to 45 minutes. For example, the mixing step (d) is performed for 30 minutes + -5 minutes.

Also within the scope of the invention, for example, in the case where the solid support is provided in dry form and the platinum reagent is provided in pure form, or in the case where the solids content or the brookfield viscosity of the mixture is intended to be adjusted to a particular value, the suitable solvents described in optional step (f) can be added in process step (c).

According to one embodiment of the invention, the solid content of the mixture obtained in step (c) is from 1 to 90 wt. -%, preferably from 3 to 60 wt. -%, more preferably from 5 to 40 wt. -%, most preferably from 10 to 25 wt. -%, based on the total weight of the mixture.

Optional step (g): removing at least part of the solvent

The method according to the invention may optionally comprise step (g): removing at least part of the solvent by evaporation and/or filtration and/or centrifugation and/or spray drying after step (c) and before step (d) to obtain a concentrated mixture.

As already discussed above, the mixture obtained in the contacting step (c) may comprise a solvent, for example if at least one solid support in step (a) is provided in the form of a suspension or slurry, or if at least one platinum agent in step (b) is provided in the form of a solution or suspension.

Step (g) results in a concentrated mixture containing less solvent than the mixture obtained in step (c) of contacting. In principle, the concentration step (g) can be carried out by any conventional method known to the person skilled in the art, for example by evaporation of the liquid medium and/or by filtration and/or by centrifugation and/or by spray drying.

The method selected in step (g) may depend on the nature of the solvent contained in the mixture of step (c). For example, aprotic solvents (e.g., toluene) are preferably removed by evaporation, while protic solvents (e.g., ethanol or water) are preferably removed by filtration. In other cases, a combination of initial filtration with subsequent evaporation of the residual liquid medium under reduced pressure (vacuum) may be preferred.

According to one embodiment of the invention, the method of the invention further comprises step (g): removing at least part of the solvent contained in the mixture of step (c) by evaporation. For example, the evaporation of the solvent may be performed by applying heat and/or reduced pressure using a vacuum pump.

According to another embodiment of the invention, the method of the invention further comprises step (g): removing at least part of the solvent contained in the mixture of step (c) by filtration. For example, filtration may be performed by drum filters or filter presses or by nanofiltration.

According to another embodiment of the invention, the method of the invention further comprises step (g): removing at least part of the solvent contained in the mixture of step (c) by filtration and evaporation, preferably by filtration and subsequent evaporation.

According to another embodiment of the invention, the method of the invention further comprises step (g): removing at least part of the solvent contained in the mixture of step (c) by centrifugation. For example, centrifugation and decantation of the solvent may be performed by a disk centrifuge.

According to yet another embodiment of the invention, the method of the invention further comprises step (g): removing at least part of the solvent contained in the mixture of step (c) by spray drying. For example, spray drying of the solvent may be performed in a spray dryer.

After removal of at least part of the solvent contained in the mixture of step (c), the mixture obtained in step (g) is a concentrated mixture. In a preferred embodiment, the solids content of the concentrated mixture is at least 70 wt%, preferably at least 80 wt%, more preferably at least 85 wt%, and most preferably at least 90 wt%, based on the total weight of the mixture. For example, the solids content of the concentrated mixture may be 95 wt% based on the total weight of the mixture.

According to another embodiment of the process of the present invention, the solvent comprised in the mixture of step (c) is removed in step (g) to obtain a dried mixture.

Optional step (h): heat treatment of

According to optional step (h) of the process for preparing the catalytic system of the invention, the mixture of step (c) or the concentrated mixture of optional step (g) is heat treated at a temperature of 25 to 200 ℃, preferably at a temperature of 50 to 180 ℃, most preferably at a temperature of 100 to 150 ℃.

The term "heating" or "heat treatment" does not limit the method of the invention to a method in which the temperature of the mixture is actively adjusted to a defined temperature range by the addition of energy from an external heat source. The term also includes the temperature that is maintained in an exothermic reaction, e.g. reached in the contacting step (c), during a specific period of time.

The heat treatment may be performed for a specific period of time. Thus, in one embodiment, step (h) is carried out for at least 5 minutes, preferably 0.25 to 24 hours, more preferably 1 to 5 hours, and most preferably 2 to 3 hours.

In a preferred embodiment, the mixture of step (c) or the optionally concentrated mixture of step (g) is heat treated at a temperature of 25 ℃ to 200 ℃, preferably at a temperature of 50 ℃ to 180 ℃, and most preferably at a temperature of 100 ℃ to 150 ℃, wherein the heat treatment is carried out for at least 5 minutes, preferably 0.25 hours to 24 hours, more preferably 1 hour to 5 hours, most preferably 2 to 3 hours.

In general, the optional heat treatment step may be performed using any suitable heat treatment/heating apparatus, and may for example comprise heat heating and/or heating under reduced pressure and/or drying in a vacuum chamber using apparatus such as an evaporator, flash dryer, oven, spray dryer. The optional heat treatment step may be performed under reduced pressure, ambient pressure, or elevated pressure. Preferably, the optional thermal heating step is performed at ambient pressure.

Step (d): calcination step

In step (d), the mixture of step (c) is calcined at a temperature of 200 ℃ to 600 ℃.

The term "calcination" according to the invention means a heat treatment at high temperature, which results in a partial or complete thermal conversion (partial or complete calcination) of the platinum agent. During calcination, the platinum agent containing Pt ions is partially or fully converted to Pt oxide.

According to a preferred embodiment of the present invention, the calcination step (d) is carried out at a temperature of 270 to 480 ℃, preferably at a temperature of 300 to 450 ℃ and most preferably at a temperature of 330 to 400 ℃.

The calcination step of the present invention is not limited to a step in which the temperature of the mixture is actively adjusted to a defined temperature range by adding energy from an external heat source. The calcining step further includes maintaining the temperature reached in this step for a specified period of time.

The calcination step may be performed for a specific period of time. Thus, in one embodiment, step (h) is carried out for at least 10 minutes, preferably from 0.5 to 24 hours, more preferably from 1 to 5 hours, and most preferably from 2.5 to 3.5 hours.

The calcining step can be performed in air, N ₂ Atmosphere, ar atmosphere, O ₂ The atmosphere or mixtures thereof, preferably under air.

According to a preferred embodiment of the present invention, the calcination step is carried out in air, N, at a temperature of 200 ℃ to 600 ℃, preferably at a temperature of 270 ℃ to 480 ℃, more preferably at a temperature of 300 ℃ to 450 ℃ and most preferably at a temperature of 330 ℃ to 400 °c ₂ Atmosphere, ar atmosphere, O ₂ Under an atmosphere or a mixture thereof.

In general, the calcination step may be performed using any suitable calcination/heating apparatus, and may, for example, include thermal heating and/or heating under reduced pressure using an apparatus such as a flash dryer or oven. Preferably, the calcination step is carried out at ambient pressure.

Optional step (e): catalytic system for reduction calcination

According to optional step (e) of the process for preparing the catalytic system of the invention, the calcined catalytic system obtained from step (d) is reacted in H ₂ At a temperature of 100 ℃ to 500 ℃ under an atmosphere And reducing to obtain a catalytic system comprising elemental platinum, platinum oxides, and mixtures thereof.

By such a reduction step, a catalytic system is obtained comprising a platinum compound on a solid support, wherein the platinum compound is selected from the group consisting of elemental platinum, platinum oxides and mixtures thereof.

Within the meaning of the present invention, the term "reduction" refers to a chemical reaction in which the oxidation state of platinum in the platinum reagent changes from a higher oxidation state to a lower oxidation state, preferably to zero. More precisely, during the reduction step (e), the platinum reagent on the surface of the solid support undergoes a reaction in which elemental platinum, platinum oxides and mixtures thereof are obtained on the surface of at least one solid support.

The reduction step is necessary to obtain a catalytic system comprising a platinum compound on a solid support, wherein the platinum compound is selected from the group consisting of elemental Pt, platinum oxides, in particular platinum oxides having a lower oxidation state than before the reduction reaction, and mixtures thereof.

Without such a reduction step, it is not possible to obtain a platinum compound in elemental form on the surface of the solid support, or to obtain a platinum compound in a lower oxidation state than before the reduction reaction. For example, the platinum reagent comprises platinum metal in oxidation states I to VI and is reduced to a lower oxidation state or oxidation state of 0 than before the reduction reaction.

More precisely, the platinum agent comprises Pt in oxidation state Pt (I), pt (II), pt (III), pt (IV), pt (V), pt (VI) and mixtures thereof, and is reduced to Pt and mixtures thereof in oxidation state lower than at least one oxidation state prior to the reduction reaction, and preferably in oxidation state 0. For example, pt (VI) is reduced to elemental Pt, pt (I), pt (II), pt (III), pt (IV), pt (V), or mixtures thereof, pt (V) is reduced to elemental Pt, pt (I), pt (II), pt (III), pt (IV), or mixtures thereof, pt (IV) is reduced to elemental Pt, pt (I), pt (II), pt (III), or mixtures thereof, pt (III) is reduced to elemental Pt, pt (I), pt (II), or mixtures thereof, pt (II) is reduced to elemental Pt, pt (I), or mixtures thereof, and Pt (I) is reduced to elemental Pt.

In addition to the platinum compound selected from elemental platinum, platinum oxides and mixtures thereof on the surface of at least one solid support, other reactive compounds may also be present after the reduction step. These reactive compounds may be products obtained from the counter ion of a platinum salt or the ligand of a platinum complex with calcium carbonate.

Preferably, the amount of these reaction products is less than 100 wt. -% based on the dry weight of the platinum compound on the surface of the at least one solid support, more preferably less than 80 wt. -%, even more preferably less than 50 wt. -%, even more preferably less than 30 wt. -% and most preferably less than 10 wt. -% based on the dry weight of the platinum compound on the surface of the at least one solid support.

According to a preferred embodiment of the invention, the catalytic system consists solely of at least one solid support and a platinum compound on the surface of said support, wherein the platinum compound is selected from the group consisting of elemental platinum, platinum oxides and mixtures thereof.

Reduction step (d) at H ₂ Under atmosphere, which means H ₂ Comprising 5 to 99.95 volume% H based on the total volume of the gas ₂ Preferably 7 to 99.95 volume% H based on the total volume of the gas ₂ Even more preferably 10 to 99.90% by volume of H ₂ And most preferably 15 to 99% by volume of H ₂ . Up to 100% by volume of the remaining gas is an inert gas, such as nitrogen, argon and/or helium.

According to a preferred embodiment of the present invention, the reduction step (e) is carried out at a temperature of 100 to 500 ℃, preferably at a temperature of 300 to 450 ℃, most preferably at a temperature of 350 to 400 ℃.

The reduction step of the present invention is not limited to a step in which the temperature of the mixture is actively adjusted to a defined temperature range by adding energy from an external heat source. The reducing step further includes maintaining the temperature reached in this step for a specified period of time.

The reduction step may be performed for a specific period of time. Thus, in one embodiment, step (e) is performed for at least 10 minutes, preferably 0.5 to 24 hours, more preferably 1 to 5 hours, most preferably 2.5 to 3.5 hours.

According to a preferred embodiment of the invention, the reduction step (e) is carried out in100 ℃ to 500 ℃, preferably 200 ℃ to 475 ℃, more preferably 300 ℃ to 450 ℃, most preferably 350 ℃ to 400 ℃, at H ₂ The process is carried out under an atmosphere for at least 10 minutes, preferably 0.5 to 24 hours, more preferably 1 to 5 hours, most preferably 2.5 to 3.5 hours.

The inventors have surprisingly found that by the above method, a catalytic system can be provided wherein a platinum compound selected from the group consisting of elemental platinum, platinum oxides and mixtures thereof is on a solid support which is precipitated calcium carbonate and has a length of 15 to 100m measured using nitrogen and the BET method according to ISO 9277:2010 ² Specific surface area per gram. Furthermore, the above-described process is an inexpensive and simple preparation process, which provides the catalytic system of the present invention. In addition, by the above-described method, a catalytic system can be provided in which a platinum compound is directly prepared on the surface of a solid support, rather than being prepared before such a platinum compound is immobilized on the surface of the solid support. Since elemental platinum, platinum oxides, and mixtures thereof are prepared directly on the surface of a solid support, no additional stabilizers such as polymers are required. Furthermore, the inventors have surprisingly found that by the above method, a catalytic system can be provided wherein the platinum compound is uniformly distributed on the surface of the high surface area Precipitated Calcium Carbonate (PCC).

As described above, the method for preparing the catalytic system for platinum compounds contained on a solid support of the present invention comprises the steps of:

(a) Providing at least one solid support, wherein the solid support is Precipitated Calcium Carbonate (PCC) and has a length of 15 to 100m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area/g;

According to another embodiment of the present invention, a method for preparing a catalytic system comprising a platinum compound on a solid support comprises the steps of:

(c) Contacting at least one solid support provided in step (a) with the platinum reagent provided in step (b) to obtain a mixture comprising the solid support and the platinum reagent;

(d) Calcining the mixture of step (c) at a temperature of 200 ℃ to 600 ℃ to obtain a catalytic system comprising platinum oxide on a solid support; and

(e) At H ₂ Reducing the calcined catalytic system obtained from step (d) at a temperature of 100 ℃ to 500 ℃ under an atmosphere to obtain a catalytic system comprising elemental platinum, platinum oxides and mixtures thereof.

(d) Calcining the mixture of step (c) at a temperature of 200 ℃ to 600 ℃ to obtain a catalytic system comprising platinum oxide on a solid support;

(e) At H ₂ Reducing the calcined catalytic system obtained from step (d) at a temperature of 100 ℃ to 500 ℃ under an atmosphere to obtain a catalytic system comprising elemental platinum, platinum oxides and mixtures thereof; and

(f) Providing a solvent and contacting at least one solid support provided in step (a) and/or the platinum reagent provided in step (b) in any order before or during step (c), and preferably the solvent is a non-polar solvent, a polar solvent or a mixture thereof, more preferably the non-polar solvent is selected from pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane and mixtures thereof, and/or the polar solvent is selected from tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and mixtures thereof, even more preferably the solvent is a polar solvent, and most preferably the solvent is water.

(e) At H ₂ Reducing the calcined catalytic system obtained from step (d) at a temperature of 100 ℃ to 500 ℃ under an atmosphere to obtain a catalytic system comprising elemental platinum, platinum oxides and mixtures thereof;

(f) Providing a solvent and contacting at least one solid support provided in step (a) and/or the platinum reagent provided in step (b) in any order before or during step (c), and preferably the solvent is a non-polar solvent, a polar solvent or a mixture thereof, more preferably the non-polar solvent is selected from pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane and mixtures thereof, and/or the polar solvent is selected from tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and mixtures thereof, even more preferably the solvent is a polar solvent, and most preferably the solvent is water; and

(g) Removing at least part of the solvent by evaporation and/or filtration and/or centrifugation and/or spray drying after step (c) and before step (d) to obtain a concentrated mixture.

(f) Providing a solvent and contacting at least one solid support provided in step (a) and/or the platinum reagent provided in step (b) in any order before or during step (c), and preferably the solvent is a non-polar solvent, a polar solvent or a mixture thereof, more preferably the non-polar solvent is selected from pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane and mixtures thereof, and/or the polar solvent is selected from tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and mixtures thereof, even more preferably the solvent is a polar solvent, and most preferably the solvent is water;

(g) Removing at least part of the solvent by evaporation and/or filtration and/or centrifugation and/or spray drying after step (c) and before step (d) to obtain a concentrated mixture; and

(h) Heat treating the mixture of step (c) or the concentrated mixture of step (g) at a temperature of 25 ℃ to 200 ℃, preferably at a temperature of 50 ℃ to 180 ℃, most preferably at a temperature of 100 ℃ to 150 ℃.

Additional optional method steps

The catalytic system obtained by the process of the invention is preferably a dry product, most preferably in the form of a powder, flake, granule, particle or aggregate.

The catalytic system obtained can optionally be further processed in a milling step. In general, the milling of the catalytic system may be carried out in a dry milling or wet milling process and may be carried out with any conventional milling device, for example under conditions in which the comminution is mainly caused by impact with the second object, i.e. in one or more of the following: ball mills, rod mills, vibration mills, roller crushers, centrifugal impact mills, vertical bead mills, attritors, pin mills, hammer mills, crushers, pulpers, chopper (de-chopper), knife cutters, or other such devices known to those skilled in the art.

In the case of grinding as wet grinding, the ground catalytic system can then be dried. In general, drying may be performed using any suitable drying apparatus, and may include, for example, thermal heating and/or heating under reduced pressure and/or drying in a vacuum chamber using apparatus such as an evaporator, flash dryer, oven, spray dryer. Drying may be carried out under reduced pressure, ambient pressure or elevated pressure. Preferably, the drying is carried out at ambient pressure.

The catalytic system obtained by the process of the invention can be further alloyed with lead, sometimes colloquially referred to as "poisoning". Such alloying is known to the person skilled in the art, for example from the preparation of Lindlar catalysts. Without being bound by any theory, it is believed that lead acts to deactivate the platinum sites, preventing the formation of alkanes. Thus, if a compound contains a triple bond, it is reduced to a double bond only. One example is the reduction of phenylacetylene to styrene.

According to one embodiment of the invention, the process of the invention for preparing a catalytic system comprising a platinum compound on a solid support comprises the following steps:

(b') providing at least one lead reagent comprising Pb ions in an amount such that the amount of said ions is from 0.1 to 15% by weight based on the dry weight of said solid support,

(d) Calcining the mixture of step (c) at a temperature of 200 ℃ to 600 ℃ to obtain a catalytic system comprising a platinum oxide on a solid support, and

(d ') contacting the catalytic system of step (d) with the lead reagent provided in step (b') to obtain a catalytic system having Pb on the surface of the catalytic system.

The lead reagent used in step b') may be any lead reagent known to the skilled person. Preferably, the lead reagent is a water-soluble lead reagent. According to a preferred embodiment, the lead reagent is (CH ₃ COO) ₂ Pb。

Catalytic system

By the process of the invention, the catalytic system of the invention is obtained. The catalytic system according to the invention comprises a platinum compound on a solid support, wherein

a) The solid support is a Precipitated Calcium Carbonate (PCC) and has a length of 15 to 100m measured using nitrogen and BET method according to ISO 9277:2010 ² Specific surface area/g; and

In general, the catalytic system of the invention consists of a particulate solid support material (precipitated calcium carbonate) and platinum compounds (elemental platinum and/or platinum oxides) present on at least part of the accessible surfaces of said support material. The platinum species is present on the surface of the solid support at 0.1 to 15 wt% based on the dry weight of the solid support.

Specific embodiments of the solid support have been described above in step (a) of the process of the invention and are therefore suitable for use in the solid support and platinum compounds of the catalytic system of the invention.

The solid support is precipitated calcium carbonate, preferably having aragonite, vaterite or calcite crystal forms, and mixtures thereof.

According to one embodiment, the solid support has:

According to another embodiment, the solid support has:

(i) Between 20 and 90m measured using nitrogen and BET method according to ISO 9277:2010 ² /g, preferably 25 to 80m ² /g, more preferably 30 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g; or (b)

(ii) D in the range of 1 to 75 μm, preferably 2 to 50 μm, more preferably 3 to 40 μm, even more preferably 4 to 30 μm, most preferably 5 to 15 μm ₅₀ (wt); or (b)

According to another embodiment, the solid support has:

(i) Between 15 and 100m measured using nitrogen and BET method according to ISO 9277:2010 ² /g, preferably 20 to 90m ² /g, preferably 25 to 80m ² /g, more preferably 30 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g; and

(ii) D in the range of 1 to 75 μm, preferably 2 to 50 μm, more preferably 3 to 40 μm, even more preferably 4 to 30 μm, most preferably 5 to 15 μm ₅₀ (wt); and

Specific embodiments of the platinum compounds have been described in step (e) of the process of the invention hereinabove, and will therefore be suitable for use in the solid support of the catalytic system of the invention and the platinum compounds.

According to one embodiment of the invention, the platinum compound is selected from the group consisting of elemental platinum, ptO ₂ 、PtO ₃ And mixtures thereof, preferably selected from the group consisting of elemental platinum, ptO ₂ And mixtures thereof, most preferably elemental platinum.

According to another embodiment of the present invention, the content of platinum species on the surface of the solid support is in the range of 0.25 to 13 wt%, preferably 0.5 to 11 wt%, more preferably 1.0 to 10.0 wt%, even more preferably 1.5 to 8.0 wt%, and most preferably 2.0 to 7.0 wt%, based on the dry weight of the solid support.

According to another embodiment of the invention, the catalytic system according to the invention is in the form of a powder, a flake, a granule, a particle or an aggregate, and preferably in the form of a particle, and has:

According to another embodiment of the invention, the catalytic system according to the invention is in particulate form and has:

(i) Between 15 and 80m measured using nitrogen and BET method according to ISO 9277:2010 ² /g, preferably 20 to 75m ² /g, more preferably 25 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g; or (b)

(ii) In a range of 1 to 75 μm, preferably 2 to 50 μm, more preferably 3 to 40 μm, even more preferably 4 to 30 μm,and most preferably d in the range of 5 to 15 μm ₅₀ (wt); or (b)

(i) Between 15 and 80m measured using nitrogen and BET method according to ISO 9277:2010 ² /g, preferably 20 to 75m ² /g, more preferably 25 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g; and

The inventors have found that the catalytic system according to the invention has several advantages. First of all, the precipitated calcium carbonate according to the invention has been found to be particularly useful as a support material in catalysis. In particular, it has been found that in combination with platinum compounds such as described above, higher catalytic activity, e.g. higher phenylacetylene conversion under hydrogen, can be obtained using the catalytic system according to the present invention.

The catalytic system according to the invention comprises a platinum compound on a solid support, wherein

a) The solid support is Precipitated Calcium Carbonate (PCC) and has a particle size of 15 to 100m measured using nitrogen and BET method according to ISO9277:2010 ² Specific surface area/g; and is also provided with

According to another embodiment of the invention, the catalytic system according to the invention comprises a platinum compound on a solid support, wherein

and wherein the content of platinum species on the solid support surface is from 0.25 to 13 wt%, preferably from 0.5 to 11 wt%, more preferably from 1.0 to 10.0 wt%, even more preferably from 1.5 to 8.0 wt%, and most preferably from 2.0 to 7.0 wt%, based on the dry weight of the solid support.

and wherein the content of platinum species on the surface of the solid support is from 0.1 to 15 wt% based on the dry weight of the solid support,

wherein the catalytic system is in particulate form and has:

(i) Between 15 and 80m measured using nitrogen and BET method according to ISO9277:2010 ² /g, preferably 20 to 75m ² /g, more preferably 25 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g; and

wherein the catalytic system is in the form of particles and has a particle size of 15 to 80m, measured using nitrogen and BET method according to ISO9277:2010 ² /g, preferably 20 to 75m ² /g, more preferably 25 to 70m ² /g, and most preferably 35 to 60m ² Specific surface area in the range of/g.

According to another embodiment, the catalytic system according to the invention has a length of 0.001 to 2.3cm measured using the BJH method according to BS4359-1:1996 ³ /g, more preferably 0.01 to 1.5cm ³ Preferably 0.02 to 1.0cm ³ /g, most preferably 0.02 to 0.5cm ³ Specific pore volume of intraparticle intrusion per gram.

Additionally or alternatively, the intra-particle pore size of the catalytic system according to the invention, measured using the BJH method according to BS 4359-1:1996, is in the range of 0.004 to 1.6 μm, more preferably in the range of 0.005 to 1.0 μm, especially preferably 0.006 to 0.80 μm, and most preferably 0.007 to 0.50 μm, for example 0.010 to 0.10 μm.

According to another embodiment of the invention, the catalytic system according to the invention comprises a platinum compound and a lead compound on a solid support, wherein

b') wherein the lead compound is selected from elemental lead, lead oxides and mixtures thereof;

wherein the content of platinum species on the surface of the solid support is from 0.1 to 15 wt% based on the dry weight of the solid support; and is also provided with

Wherein the content of lead species on the surface of the solid support is from 0.1 to 15% by weight based on the dry weight of the solid support.

Use of the catalytic system of the invention in catalysis

According to one aspect of the present invention, a solid support as described above, on which the platinum compound as described above is supported, is used as a catalyst.

The catalytic system of the present invention finds particular utility in a number of catalytic reactions. For example, styrene is known as a starting material for many products, achieving higher yields in phenylacetylene conversion under hydrogen, allowing high yields of styrene to be obtained.

Accordingly, one aspect of the present invention relates to the use of the catalytic system of the present invention in a process comprising the steps of:

(A) Providing one or more reactants;

(B) Providing a catalytic system of the present invention;

A preferred embodiment of the present invention relates to the use of the catalytic system of the present invention in a process according to the preceding aspect, wherein the process further comprises step (D): recovering the catalytic system after the chemical reaction of step (C) and optionally recycling the catalytic system after the chemical reaction of step (C).

In a preferred embodiment of the invention, the chemical reaction in step (C) comprises heterogeneous catalysis. In a more preferred embodiment, the chemical reaction in step (C) may be selected from one or more of the following reaction types: alkene hydrogenation and alkyne hydrogenation. According to a preferred embodiment, the chemical reaction in step (C) is selected from one or more of alkyne hydrogenation.

The catalytic system of the invention can also be used in different shapes such as in the form of granules, molded articles or extrudates containing the catalytic system. Typical shapes include spheres, pellets, monoliths, honeycombs, rings, and the like.

The particles are prepared by crushing and sieving the gel to obtain the desired size or by drying the precipitated paste and binder. Optionally, the granulation process further comprises a heat treatment to achieve specific physical properties. The particle size of the particles is typically 40 microns to a maximum of 1 cm.

The molded article is a hollow form having a specific shape obtained from some substances in an extensible state.

The extrudate is formed by pushing the paste through a die, cutting to length, drying, and optionally calcining.

Drawings

The scope and the benefit of the present invention may be better understood based on the following examples, which are intended to illustrate embodiments of the present invention.

Figure 1 shows the performance evaluation from the catalytic conversion of phenylacetylene to styrene and ethylbenzene and the yields of styrene and ethylbenzene for different Pt/PCC catalysts.

FIG. 2 shows performance evaluations of catalytic conversion of phenylacetylene to styrene and ethylbenzene and yields of styrene and ethylbenzene for different Pb-Pt/PCC catalysts.

FIG. 3 shows styrene yields as a function of BET surface area for different Pt/PCC catalysts and Pb-Pt/PCC catalysts.

Detailed Description

Experimental part

1. Measurement method

The parameters given in the examples and claims were evaluated using the following measurement methods.

BET Specific Surface Area (SSA) of the material

The BET specific surface area is measured using nitrogen via the BET method according to ISO 9277:2010, followed by conditioning the sample by heating at 250 ℃ for a period of 30 minutes. Prior to making such measurements, the samples were filtered, rinsed and dried in an oven at 110 ℃ for at least 12 hours.

Particle size distribution of particulate material (weight% of particles with diameter < X), d ₅₀ Values (weight median particle diameter) and d ₉₈ Value:

the weight median particle diameter is determined by sedimentation, which is an analysis of the sedimentation behavior in a gravitational field. By Sedigraph Micromeritics Instrument Corporation ^TM 5120 a measurement is made. The method and apparatus are known to the skilled person and are generally used to determine the grain size of fillers and pigments. Measured at 0.1 wt% Na ₄ P ₂ O ₇ In aqueous solution. The samples were dispersed and sonicated using a high speed stirrer.

The methods and instruments are known to those skilled in the art and are generally used to determine the grain size of fillers and pigments.

Porosity/pore volume/pore size

Porosity or pore volume and pore size were measured using the BJH method according to BS 4359-1:1996. Prior to making this measurement, the sample was filtered, rinsed and dried in an oven at 110 ℃ for at least 12 hours.

2. Material and apparatus

Materials and reagents

The following chemicals and materials were purchased at the highest purity grade available and used without further purification: phenylacetylene (Alfa Aesar, 98+%) styrene (Alfa Aesar, 99%), ethylbenzene (Alfa Aesar, 99%), cyclohexane (Innochem, 99.5%), ethanol (Innochem, AR, 95%), mesitylene (Alfa Aesar, 98+%) ethyl acetate (sinpharm, AR), deuterated chloroform (Innochem, 99.8 at.% D), platinum chloride (Bidei, 97%), hydrochloric acid (sinpharm, 37%), sodium formate (Macklin, 99.5%), lead acetate (aladin, 99%), 5 wt.% Pt/CaCO3 (BASF, AR).

The following Precipitated Calcium Carbonate (PCC) was prepared and used:

PCC-04

a commercially available precipitated calcium carbonate is available from Omya International AG, switzerland. PCC-04 is a triangleFacer PCC and has 4.3m ² Specific surface area per gram.

PCC-21

Milk of lime is prepared by mixing calcium oxide with water for 15 to 30 minutes under mechanical agitation. The ratio of calcium oxide to water is 1:5. Thereafter, 0.05 wt% (active/dry) sucrose (as a 64 wt% solution) was added. The resulting milk of lime has a solids content of 13% by weight, based on the total weight of the milk of lime.

The lime milk obtained was transferred to a stainless steel reactor, to which was added 0.02 wt% (active/dry) sucrose (as a 64 wt% solution). The temperature of the milk of lime was adjusted to 30 ℃. By introducing air/CO ₂ Mixture (20 vol% CO) ₂ ) The lime milk is carbonated. During the carbonation step, the reaction mixture was stirred at 1400 rpm. The kinetics of the reaction was monitored by online pH and conductivity measurements. The solids content of the resulting colloidal PCC was 16 wt.% based on the total weight of the resulting colloidal PCC suspension.

The resulting colloidal PCC suspension was then dewatered by using a membrane filter press to give a filter cake with a solids content of 55 wt.%. The filter cake was then thermally dehydrated to a dried product (solids content > 97 wt%) using a flash dryer. The specific surface area of the PCC obtained was 21.4m ² /g。

PCC-30

Milk of lime is prepared by mixing calcium oxide with water for 15-30 minutes under mechanical agitation. The ratio of calcium oxide to water is 1:5. Thereafter, 0.04 wt% (active/dry) sucrose (as a 64 wt% solution) was added. The resulting milk of lime has a solids content of 13% by weight, based on the total weight of the milk of lime.

The resulting milk of lime was transferred to a stainless steel reactor and the temperature of the milk of lime was adjusted to 18 ℃. The solids content of the milk of lime was adjusted to 10% by weight by adding water while transferring it. By introducing air/CO ₂ Mixture (20 vol% CO) ₂ ) The lime milk is carbonated. During the carbonation step, the reaction mixture was stirred at 1400 rpm. Monitoring by on-line pH and conductivity measurementsKinetics of the reaction. The solids content of the resulting colloidal PCC was 12 wt.% based on the total weight of the resulting colloidal PCC suspension.

The resulting colloidal PCC suspension was then dewatered by using a membrane filter press to give a filter cake with a solids content of 55 wt.%. The filter cake was then thermally dehydrated to a dried product (solids content > 97 wt%) using a flash dryer. The PCC obtained had a specific surface area of 30.7m ² /g。

PCC-60

A commercially available precipitated calcium carbonate is available from Omya International AG, switzerland. PCC-60 is colloidal PCC, having a particle size of 60.6m ² Specific surface area per gram.

Preparation of the catalytic System

The catalytic system was prepared analogously to the synthesis protocol originally reported by Lindlar et al (Lindlar, H.; dubuis, R.; 1966); palladium Catalyst for Partial Reduction of Acetylenes ". Organic Synthesis.46:89; lindlar, H.; month 1.2 in 1952); ein neuer Katalysator f U r selektive Hydrierungen". Helvetica Chimica acta.35 (2): 446-450.)

In the first step, 0.23mmol PtCl was added ₄ Into a 10mL Erlenmeyer flask, 0.2mL of 37% hydrochloric acid was added. The flask was stirred at about 30℃until PtCl ₄ Completely dissolved.

The resulting chloroplatinic acid solution was transferred to a 10mL beaker containing 2.5mL of distilled water, to which 3mol/L aqueous sodium hydroxide solution was slowly added so that the pH of the solution was 4.0 to 4.5. Then, 5.5mL of the resulting solution was added to a 10mL three-necked round bottom flask equipped with a thermometer and partially immersed in a water bath. Then, 1g of the corresponding PCC solid support was added, the well-stirred suspension was heated to 75-85℃and maintained at that temperature until all Pt had precipitated; this takes about 15 minutes. While maintaining the mixture at 75-85 ℃, 330 μl of HCOONa solution at a concentration of 0.7mol/L was added and stirred for 40 minutes, then 250 μl of HCOONa solution at a concentration of 0.7mol/L was added and stirred for another 40 minutes. Subsequently, the desired amount of deionized water was added and centrifuged several times, and finally, the resulting material was dried in an oven at 60 ℃ overnight.

The Pb-containing catalytic system is prepared by the following scheme:

a 10mL three-necked round bottom flask was used, equipped with a thermometer and partially immersed in a water bath. The wet catalytic system obtained by the above procedure was placed in a 10mL round bottom flask and heated with stirring to a temperature of 85 ℃ before drying, then 3.3mL of deionized water and 1mL of 7.7 wt% (CH ₃ COO) ₂ Pb solution, and the resulting mixture was stirred at 85℃for 40 minutes. Finally, the catalytic system obtained is washed centrifugally by adding deionized water and dried in an oven at 60 ℃.

The resulting catalytic system is described in the following table. All catalytic systems contained 5 wt.% of platinum species on the solid support surface, based on the dry weight of the solid support:

^a surface area (S) _BET ) Measured via the BET method according to ISO 9277:2010 using nitrogen.

^b Determined by the BJH method according to BS 4359-1:1996.

^c BET is performed on the lead impregnated material.

^d Is not reduced.

Catalytic research and results

Catalytic hydrogenation was carried out in a 250mL Wattech autoclave, 110. Mu.L phenylacetylene (1 mmol), 5mg of the catalytic system and solvent (3 mL cyclohexane) were introduced into the reactor. By H ₂ After 3 purges, H was purged at ambient temperature ₂ Filled to 20 bar. The reaction temperature and reaction time were maintained with strong magnetic stirring as needed. After the reaction, the batch reactor was cooled to room temperature and the product was separated from the catalyst by filtration. Mesitylene was added as an internal standard and then diluted with ethyl acetate. Finally, the collected sample solution was determined by gas chromatography-mass spectrometry (GCMS-QP 2010 SE) and purified by gas chromatography (GC-2014) using an hpinowax capillary column (30 m x 0). 250 mm. Times.0.25 μm). The GC detection conditions were as follows: nitrogen as a carrier gas; sample inlet temperature: 350 ℃; detector (FID) temperature: 300 ℃; column temperature: 50℃and heating to 250℃at a heating rate of 6℃per minute. For some substrates, 1H NMR was used for quantification or the product was isolated for quantification. Mesitylene was used as an internal standard to quantify conversion and product yield. The experiment was repeated three times, the data being the average, the experimental error being less than 1%.

Conversion (%) = [ molar amount of phenylacetylene after 1-reaction/molar amount of phenylacetylene in starting material ] ×100%

Yield (%) = molar amount of styrene product/molar amount of phenylacetylene in starting material x 100%

The catalytic system obtained was evaluated in catalytic conversion using phenylacetylene as starting molecule. The phenylacetylene chemical conversion was carried out under a hydrogen atmosphere at 20 bar and 55℃for 6 hours. This procedure was performed using an automated high throughput reactor system, wattech autoclave. Phenylacetylene is converted to styrene and ethylbenzene during the reaction.

As can be seen from fig. 2, the catalytic system alloyed with Pb of the invention shows improved performance in the reaction of phenylacetylene to styrene compared to the catalytic system of the prior art comprising PCC of low specific surface area.

As can be seen from FIG. 2, the Pt-Pb/PCC 21, pt-Pb/PCC-30 and Pt-Pb/PCC-60 catalysts (i.e., high surface area) provide about 60% to > 90% conversion and about 40% to about 70% styrene yield. In contrast, the low surface area catalyst (Pt-Pb/PCC-04) only provided poor conversion and selectivity; whereas complete conversion was observed in the absence of Pb.

When Pb is externally added to the commercial Pt/CaCO ₃ In the material, the relative selectivity to styrene increased (29% yield in the case of Pb and no styrene in the case of Pb), but the total conversion also decreased sharply (48% conversion in the case of Pb and 100% conversion in the case of Pb). This basically means that Pb has a detrimental effect on the catalytically active sites in the low surface area material.

In fig. 3, the yield of hemihydrogenated styrene is plotted as a function of specific surface area. As the specific surface area of the PCC support increases, the yield of styrene also gradually increases, which does confirm this correlation.

Furthermore, as can be seen from fig. 1, the catalytic system of the present invention produces a fully hydrogenated ethylbenzene product. In the case of Pt/PCC-60, styrene can be obtained even without addition of Pb.

Claims

1. A catalytic system comprising a platinum compound on a solid support, wherein

2. The catalytic system of claim 1, wherein the solid support has:

3. The catalytic system of any of the preceding claims, wherein the platinum compound is selected from elemental platinum, ptO ₂ 、PtO ₃ And mixtures thereof, preferably selected from the group consisting of elemental platinum, ptO ₂ And mixtures thereof, and most preferably elemental platinum.

4. The catalytic system according to any of the preceding claims, wherein the content of platinum species on the surface of the solid support is in the range of 0.25 to 13 wt. -%, preferably 0.5 to 11 wt. -%, more preferably 1.0 to 10.0 wt. -%, even more preferably 1.5 to 8.0 wt. -%, and most preferably 2.0 to 7.0 wt. -%, based on the dry weight of the solid support.

5. The catalytic system of any one of the preceding claims, wherein the catalytic system is in particulate form and has:

6. A process for preparing a catalytic system comprising a platinum compound on a solid support, the process comprising the steps of:

7. The method of claim 6, wherein the method further comprises step (e): at H ₂ Reducing the calcined catalytic system obtained from step (d) at a temperature of 100 ℃ to 500 ℃ under an atmosphere to obtain a catalytic system comprising elemental platinum, platinum oxides and mixtures thereof.

8. The process according to claim 6 or 7, wherein the calcination step (d) is performed under the following conditions:

(ii) At a temperature of 270 ℃ to 480 ℃, preferably at a temperature of 300 ℃ to 450 ℃, and most preferably at a temperature of 330 ℃ to 400 ℃.

9. The method according to any one of claims 6 to 8, wherein the method further comprises step (f): providing a solvent and contacting at least one solid support provided in step (a) and/or the platinum reagent provided in step (b) in any order before or during step (c), and preferably the solvent is a non-polar solvent, a polar solvent or a mixture thereof, more preferably the non-polar solvent is selected from pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1, 4-dioxane, chloroform, diethyl ether, dichloromethane and mixtures thereof, and/or the polar solvent is selected from tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and mixtures thereof, even more preferably the solvent is a polar solvent, most preferably the solvent is water.

10. The method of claim 9, wherein the method further comprises step (g): removing at least part of the solvent by evaporation and/or filtration and/or centrifugation and/or spray drying after step (c) and before step (d) to obtain a concentrated mixture.

11. The method according to any one of claims 9 to 10, wherein the method further comprises step (h): heat treating the mixture of step (c) or the concentrated mixture of step (g) at a temperature of 25 ℃ to 200 ℃, preferably at a temperature of 50 ℃ to 180 ℃, and most preferably at a temperature of 100 ℃ to 150 ℃.

12. The method of any one of claims 6 to 11, wherein the platinum reagent is selected from KPt (NH ₃ )Cl ₃ 、Pt(NH ₃ ) ₂ Cl ₂ 、K[(H ₂ C＝CH ₂ )PtCl ₃ ]·xH ₂ O、Na ₂ PtCl ₆ 、Pt(acac) ₂ 、Na ₂ PtCl ₄ 、H ₂ PtCl ₆ 、(NH ₄ ) ₂ [PtCl ₆ ]、PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof, preferably selected from Na ₂ PtCl ₆ 、Pt(acac) ₂ 、Na ₂ PtCl ₄ 、H ₂ PtCl ₆ 、(NH ₄ ) ₂ [PtCl ₆ ]、PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof, and most preferably selected from PtCl ₄ 、Pt(NO ₃ ) ₄ And mixtures thereof.

13. Use of the catalytic system according to any one of claims 1 to 5 in a process comprising the steps of:

(A) Providing one or more reactants;

(B) Providing a catalytic system according to any one of claims 1 to 5;

(C) In the presence of the catalytic system provided in step (B), at a temperature of 50 to 300 ℃, at H ₂ Atmosphere or inert atmosphere and H ₂ Subjecting the one or more reactants provided in step (a) to a chemical reaction in a liquid or gas phase under a combination of atmospheres.

14. The use of claim 13, wherein the method further comprises step (D): recovering and optionally recycling the catalytic system after the chemical reaction of step (C).

15. The use according to claim 13 or 14, wherein the chemical reaction in step (C) is selected from one or more of alkene hydrogenation and alkyne hydrogenation, and preferably from one or more of alkyne hydrogenation.

16. Use of a solid support as defined in any one of claims 1, 2 or 5, supported with a platinum compound as defined in any one of claims 1, 3, 4 and 5 as a catalyst.

17. Granules, mouldings or extrudates comprising the catalytic system according to any of claims 1 to 5.