Catalyst for preparing methanol through low-temperature CO2 hydrogenation as well as preparation and application of catalyst

Abstract

The invention relates to a catalyst for preparing methanol through low-temperature CO2 hydrogenation as well as preparation and application of the catalyst. A first aspect of the present application relates to a modified support prepared by: a) preparing a support using a composition comprising a metal source and a silicon source; and b) treating the carrier in step a) with a surfactant to form the modified carrier. The invention further relates to a preparation method of the modified carrier. The invention relates to a catalyst in a third aspect. The catalyst is prepared by the following steps: i) loading a catalyst active component precursor on the modified carrier in the first aspect of the application; and ii) subjecting the product of step i) to roasting. The fourth aspect of the invention relates to a preparation method of the catalyst.

Description

Technical Field

[0001] The present application relates to the field of catalysts, and more specifically to a catalyst for producing methanol by low-temperature CO2 hydrogenation, a method for preparing the catalyst, and uses of the catalyst. Background Art

[0002] Capturing CO2 and converting it into high-value chemicals and energy carriers is of great significance in helping to solve environmental and energy problems under the background of "dual carbon". Among them, using green H2 to hydrogenate CO2 to synthesize methanol is one of the ways with the lowest carbon footprint, and CO2 hydrogenation catalyst is the key to achieving CO2 hydrogenation to synthesize methanol.

[0003] CO2 has high thermodynamic stability and kinetic inertness, and requires a higher temperature to activate. However, increased temperature will promote side reactions, resulting in reduced selectivity for methanol. Obviously, high pressure and low temperature are more conducive to the CO2 hydrogenation to methanol reaction.

[0004] Cu / ZnO / Al2O3 catalyst is the most widely used industrial catalyst with good conversion rate and selectivity. However, sintering is prone to occur when using Cu / ZnO / Al2O3 catalyst, and the byproduct water in the reaction process aggravates the deactivation of Cu-based catalyst.

[0005] Therefore, improving the catalyst preparation method, finding suitable carriers or additives to improve the dispersion of the active component Cu, stimulating the activity of Cu-based catalysts and extending their life are of great significance for making the CO2 hydrogenation to methanol reaction efficient and direct.

[0006] Professor Ye Runping of Nanchang University, Professor Zhang Riguang of Taiyuan University of Technology, Dr. Melis S. Duyar of the University of Surrey, Professor Jiang Zheng of the University of Science and Technology of China, and Professor Liu Jian of Inner Mongolia University, have prepared a Cu / Zn-O-rich nanostructured carbon nanotube by in-situ substitution of Cu and Zn into the Ce-MOF (MOF, metal-organic framework material) precursor. V -Ce active site Ce-CuZn catalyst. At 260 °C, 2.8 MPa and space velocity 20000 mL·gcat -1 ·h -1 Under the condition of 100 mol / l, the methanol selectivity of the catalyst reached 71.1%. However, the preparation process of the catalyst is relatively complicated, and the production cost of MOF is relatively high, which is not conducive to large-scale industrial production (Nat. Commun., 2024, 15, 2159.)

[0007] Chinese patent application CN115770612 A provides a method for preparing a catalyst for preparing methanol by hydrogenating carbon dioxide. In this patent application, SPP molecular sieve is used as a carrier, and CuO and ZnO are used as active components. CuO accounts for 9.6-41.5% by weight in the catalyst, and ZnO accounts for 4.5-18.0% by weight. The catalyst obtained in this patent application has highly dispersed CuO and ZnO particles, and the mesopores in the SPP molecular sieve limit the particle size of the CuO and ZnO particles. The catalyst obtains a higher CO2 conversion rate and an optimal methanol space-time yield at 280°C. However, the catalyst activity is low at low temperatures (≤200°C), and the CO2 conversion rate is ≤2.5%.

[0008] Chinese patent application CN117101669A reports a copper-based catalyst containing Ge as a promoter, its preparation method and application. The inventor of the patent application used NaOH as a precipitant and hydrothermally synthesized the metal oxide carrier CeO2 by precipitation method, and then impregnated Cu(NO3)2·3H2O solution containing active metal copper and GeCl4 solution containing Ge as a promoter, and then obtained the copper-based catalyst containing Ge as a promoter by tableting and crushing. The introduction of metal Ge changes the surface acidity and alkalinity and structural properties of the catalyst, improves the strong interaction between the metal and the carrier, and promotes the adsorption and activation of CO2 on the catalyst surface. The catalyst can achieve higher methanol selectivity, but the CO2 single-pass conversion rate is less than 10%, and the reaction temperature is relatively high, at 260°C.

[0009] Although the existing technology has improved the dispersion of copper and the strong interaction between the metal and the carrier to a certain extent, thereby improving the methanol selectivity, the reaction temperature in the existing technology is relatively high, resulting in huge energy consumption and sintering of copper in the catalyst, which in turn causes the collapse of the pore structure in the catalyst, a sharp decrease in surface area, or grain agglomeration and growth, resulting in a significant decrease in catalyst performance.

[0010] Therefore, there is still a need for a CO2 hydrogenation to methanol catalyst and / or a preparation process for a CO2 hydrogenation to methanol catalyst that can overcome the defects of the prior art, so that the CO2 hydrogenation to methanol catalyst can achieve high CO2 conversion rate and methanol selectivity at a lower temperature. Summary of the invention

[0011] The present invention provides a modified carrier treated with a surfactant, a CO2 hydrogenation to methanol catalyst based on the modified carrier, and a preparation method of the modified carrier and the CO2 hydrogenation to methanol catalyst. The CO2 hydrogenation to methanol catalyst of the present application has the advantages of high dispersion of active components, high reaction activity, high selectivity of target products, and low reaction temperature.

[0012] Specifically, the first aspect of the present application relates to a modified carrier, which is prepared by the following steps:

[0013] a) preparing a carrier using a composition comprising a metal source and a silicon source;

[0014] b) treating the carrier in step a) with a surfactant to form the modified carrier;

[0015] The surfactant is selected from one or more of organic ammonium salts, organic carboxylates, organic sulfonates and polymer surfactants.

[0016] The second aspect of the present application relates to a method for preparing the modified carrier described in the first aspect of the present application, the method comprising the following steps:

[0017] a) preparing a carrier using a composition comprising a metal source and a silicon source;

[0018] b) treating the carrier in step a) with a surfactant to form the modified carrier;

[0019] The surfactant is selected from one or more of organic ammonium salts, organic carboxylates, organic sulfonates and polymer surfactants.

[0020] The third aspect of the present application relates to a catalyst, which is prepared by the following steps:

[0021] i) supporting a catalyst active component precursor on the modified carrier as described in the first aspect of the present application; and

[0022] ii) subjecting the product of step i) to calcination.

[0023] The fourth aspect of the present application relates to a method for producing the catalyst as described in the third aspect of the present application, the method comprising the following steps:

[0024] i) supporting a catalyst active component precursor on the modified carrier as described in the first aspect of the present application; and

[0025] ii) subjecting the product of step i) to calcination.

[0026] The fifth aspect of the present application relates to a method for producing methanol by hydrogenating carbon dioxide, wherein the method uses the catalyst described in the third aspect of the present application.

[0027] The sixth aspect of the present application relates to the use of the catalyst described in the third aspect of the present application in a process for producing methanol by hydrogenation of carbon dioxide.

[0028] The applicant of the present application has unexpectedly found that by using an alkaline carrier and pre-treating the carrier with a surfactant before loading the active component, a desired CO2 hydrogenation to methanol catalyst can be prepared: the CO2 hydrogenation to methanol catalyst can simultaneously achieve a high CO2 conversion rate and methanol selectivity at a relatively low temperature (e.g., ≤200°C), and simultaneously achieve a high methanol + CO selectivity. The generated CO can provide energy for CO2 hydrogenation to methanol, thereby further reducing the energy consumption of the reaction, making the reaction more environmentally friendly and green, and improving the economic benefits of the reaction process. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Exemplary embodiments will now be described more fully with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. However, the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided to make this disclosure comprehensive and complete and to fully convey the ideas of the invention to those skilled in the art. Like reference numerals represent like elements.

[0030] Figure 1 For exemplary purposes, a preparation process of a catalyst according to one embodiment of the present invention is shown;

[0031] Figure 2 is the X-ray diffraction (XRD) pattern of the catalyst prepared in Example 1 of the present application;

[0032] Figure 3 This is a transmission electron microscope (TEM) image of the catalyst prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0033] "Scope" disclosed herein is defined in the form of lower limit and upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a particular range. The scope defined in this way can be inclusive or exclusive of end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following range can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In this application, unless otherwise specified, the numerical range "a to b" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0 to 5" means that all real numbers between "0 to 5" are listed in this document, and "0 to 5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0034] In this application, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0035] In this application, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0036] In the present application, unless otherwise specified, all steps mentioned herein may be performed sequentially or randomly, but are preferably performed sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0037] In this application, unless otherwise specified, the terms "include" and "comprising" mentioned herein may be open-ended or closed-ended. For example, the terms "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0038] In the description of this article, it should be noted that, unless otherwise specified, "above" and "below" are inclusive of the number itself, and "several" in "one or several" means two or more.

[0039] In the description herein, unless otherwise specified, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0040] Herein, if there is no special explanation, the terms "a" and "an" used in the specification refer to "at least one".

[0041] Herein, unless otherwise specified, percentage (%) or part refers to percentage by weight or part by weight relative to the composition.

[0042] Herein, unless otherwise stated, the sum of the contents of the various components in the composition is 100%.

[0043] Herein, unless otherwise specified, the sum of the parts of each component in the composition may be 100 parts by weight.

[0044] In this document, unless otherwise specified, "a combination thereof" means a multi-component mixture of the elements described, for example a mixture of two, three, four and up to the maximum possible multi-component mixture.

[0045] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0046] It should be understood that although the term first, second, third and other counts can be used to describe various elements, components, regions, layers and / or parts in this article, these elements, components, regions, layers and / or parts should not be limited by these terms. These terms are only used to distinguish an element, component, region, layer and / or part from another element, component, region, layer and / or part. Therefore, without departing from the teaching of exemplary embodiments, the first element, component, region, layer or part discussed below can be referred to as the second element, component, region, layer or part.

[0047] Unless otherwise defined, all terms (including technical and scientific terms) used in this article have the same meaning as commonly understood by ordinary technicians in the field to which the present invention belongs. It should also be understood that terms, such as those defined in commonly used dictionaries, should be interpreted as their meanings consistent with their meanings in the context of the relevant art and the present disclosure, and unless clearly defined in this article, the terms will not be interpreted in an idealized or excessive formal sense.

[0048] In the context of this application, if the term "carrier" is used alone without the modifier "modified", the term "carrier" means a carrier that has not been modified by a surfactant, and can be used interchangeably with the terms "original carrier" and "precedent carrier".

[0049] In the context of the present application, the term "modified carrier" means a carrier treated with a surfactant, and can be used interchangeably with the terms "surfactant modified carrier" and "surfactant-treated carrier".

[0050] Modified carrier

[0051] The first aspect of the present application relates to a modified carrier, which is prepared by the following steps:

[0052] a) preparing a carrier using a composition comprising a metal source and a silicon source;

[0053] b) treating the carrier in step a) with a surfactant to form the modified carrier;

[0054] The surfactant is selected from one or more of organic ammonium salts, organic carboxylates, organic sulfonates and polymer surfactants.

[0055] Step a)

[0056] [Metal source]

[0057] According to one embodiment, the metal source in step a) is selected from metal salts of one or more of the following metals: alkali metals, alkaline earth metals, or transition metals.

[0058] According to one embodiment, the metal in the metal source is chosen from metals capable of forming amphoteric metal oxides. Mention may be made, as non-limiting examples, of aluminum, gallium, zinc, titanium, or zirconium.

[0059] According to one embodiment, the metal in the metal source is selected from rare earth metals, such as lanthanum, cerium, and erbium.

[0060] According to one embodiment, the metal source in step a) is selected from metal acetates, phosphates, nitrates, and hydrochlorides. According to a preferred embodiment, the metal source is selected from metal nitrates.

[0061] According to an exemplary embodiment, the metal source is selected from one or more of Al(NO3)3·9H2O, Mg(NO3)2·6H2O, Mg(NO3)2·4H2O or Ca(NO3)2·4H2O.

[0062] [Silicon source]

[0063] According to one embodiment, the silicon source in step a) is selected from silicon dioxide, silica sol, and organosiloxane.

[0064] In step a), the mass ratio of the silicon source to the metal source, based on the dry weight of each of the silicon source and the metal source, can be adjusted according to the properties of the final modified carrier and / or catalyst.

[0065] According to one embodiment, the mass ratio of the silicon source to the metal source is 0.5 to 3.0, preferably 0.8 to 2.0, preferably 0.9 to 1.7, based on the dry weight of the silicon source and the dry weight of the metal source. According to a non-limiting embodiment, the mass ratio of the silicon source to the metal source is 0.5, or 0.55, or 0.60, or 0.65, or 0.70, or 0.75, or 0.80, or 0.85, or 0.90, or 0.95, or 1.00, or 1.05, or 1.10, or 1.15, or 1.20, or 1.25, or 1.30, or 1.35, or 1.40, or 1.45, or 1.50, or 1.55, or 1.60, or 1.65, or 1.70, or 1.80. or 2.70, or 2.75, or 2.80, or 2.85, or 2.90, or 2.95, or 3.00, based on the dry weight of the silicon source and the dry weight of the metal source.

[0066] [acid]

[0067] According to a preferred embodiment, the composition in step a) of the first aspect of the present application further comprises an acid, such as an organic acid or an inorganic acid. According to a preferred embodiment, the organic acid is selected from acetic acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, and citric acid; according to a preferred embodiment, the inorganic acid is selected from hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid.

[0068] According to a preferred embodiment, step a) of the first aspect of the present application comprises the following sub-steps:

[0069] a-1) mixing a first solution comprising the metal source and optionally an acid and a second solution comprising a silicon source to obtain a mixture;

[0070] a-2) calcining the mixture from sub-step a-1).

[0071] Sub-step a-1)

[0072] The metal source, acid and silicon source described in sub-step a-1) are all as described above.

[0073] Sub-step a-1) can be implemented in any manner known to those skilled in the art.

[0074] According to one embodiment, sub-step a-1) is carried out in a water bath. Those skilled in the art will appreciate that sub-step a-2) may also be carried out in a manner other than a water bath.

[0075] According to one embodiment, sub-step a-1) is carried out at a temperature of 30 to 120° C., or 30 to 70° C., or 40 to 60° C. According to an exemplary embodiment, sub-step a-1) is carried out at a temperature of 30° C., or 35° C., or 40° C., or 45° C., or 50° C., or 55° C., or 60° C., or 65° C., or 70° C., or 75° C., or 80° C., or 85° C., or 90° C., or 95° C., or 100° C., or 105° C., or 110° C., or 115° C., or 120° C. According to an exemplary embodiment, sub-step a-1) is carried out at a temperature of 40°C, or 42°C, or 44°C, or 46°C, or 48°C, or 50°C, or 52°C, or 54°C, or 56°C, or 58°C, or 60°C, or 62°C, or 64°C, or 66°C, or 68°C, or 70°C.

[0076] According to a preferred embodiment, sub-step a-1) is performed by: dropping the first solution into the second solution, and continuing the mixing for a time t1 after the dropping is completed.

[0077] According to one embodiment, the first solution is added dropwise to the second solution for a period of 0.1 h to 8 h, or 0.2 to 4 h, or 0.5 to 2 h. For example, the first solution is added dropwise to the second solution for 0.1 h, or 0.2 h, or 0.3 h, or 0.4 h, or 0.5 h, or 0.6 h, or 0.7 h, or 0.8 h, or 0.9 h, or 1.0 h, or 1.1 h, or 1.2 h, or 1.3 h, or 1.4 h, or 1.5 h, or 1.6 h, or 1.7 h, or 1.8 h, or 1.9 h, or 2.0 h, or 2.1 h, or 2.2 h, or 2.3 h, or 2.4 h, or 2.5 h, or 2.6 h, or 2.7 h, or 2.8 h, or 2.9 h, or 3.0 h, or 3.1 h, or 3.2 h, or 3.3 h, or 3.4 h, or 3.5 h, or 3.6 h, or 3.7 h, or 3.8 h, or 3.9 h. 9h, or 4.0h, or 4.1h, or 4.2h, or 4.3h, or 4.4h, or 4.5h, or 4.6h, or 4.7h, or 4.8h, or 4.9h, or 5.0h, or 5.1h, or 5.2h, or 5.3h, or 5.4h, or 5.5h, or 5.6h, or 5.7h, or 5.8h, or 5.9h, or 6. 0h, or 6.1h, or 6.2h, or 6.3h, or 6.4h, or 6.5h, or 6.6h, or 6.7h, or 6.8h, or 6.9h, or 7.0h, or 7.1h, or 7.2h, or 7.3h, or 7.4h, or 7.5h, or 7.6h, or 7.7h, or 7.8h, or 7.9h, or 8.0h.

[0078] According to one embodiment, t1 is 1 to 48 hours, or 12 to 36 hours, or 20 to 28 hours. In non-limiting examples, t1 can be 2 hours, or 4 hours, or 6 hours, or 8 hours, or 10 hours, or 12 hours, or 14 hours, or 16 hours, or 18 hours, or 20 hours, or 22 hours, or 24 hours, or 26 hours, or 28 hours, or 30 hours, or 32 hours, or 34 hours, or 36 hours, or 38 hours, or 40 hours, or 42 hours, or 44 hours, or 46 hours, or 48 hours.

[0079] Sub-step a-2)

[0080] Sub-step a-2) involves calcining the mixture from sub-step a-1).

[0081] In a preferred embodiment, sub-step a-2) is performed by heating from room temperature to calcination temperature T1 over time t2, and maintaining at T1 for time t3.

[0082] However, those skilled in the art will appreciate that the manner of carrying out sub-step a-2) is not limited thereto.

[0083] The calcination in sub-step a-2) can be carried out in equipment familiar to those skilled in the art. For example, the calcination in sub-step a-2) can be carried out in a muffle furnace.

[0084] The temperature and duration of sub-step a-2) can be adjusted depending on the specific components and the desired support or modified support.

[0085] According to one embodiment, T1 in sub-step a-2) is 200 to 700°C, or 250 to 500°C, or 300 to 400°C. For example, T1 may be 200°C, or 210°C, or 220°C, or 230°C, or 240°C, or 250°C, or 260°C, or 270°C, or 280°C, or 290°C, or 300°C, or 310°C, or 320°C, or 330°C, or 340°C, or 350°C, or 360°C, or 370°C, or 380°C, or 390°C, or 400°C, or 410°C, or 420°C, or 430°C, or 440°C, Or 450℃, or 460℃, or 470℃, or 480℃, or 490℃, or 500℃, or 510℃, or 520℃, or 530℃, or 540℃, or 550℃, or 560℃, or 570℃, or 580℃, or 590℃, or 600℃, or 610℃, or 620℃, or 630℃, or 640℃, or 650℃, or 660℃, or 670℃, or 680℃, or 690℃, or 700℃.

[0086] According to one embodiment, time t2 is 1 to 4 hours, or 1.5 to 3 hours. For example, time t2 can be 1 hour, or 1.5 hours, or 2.0 hours, or 2.5 hours, or 3.0 hours, or 3.5 hours, or 4.0 hours.

[0087] According to one embodiment, time t3 is 2 to 8 hours, or 2 to 6 hours, or 2 to 4 hours. For example, time t3 can be 2 hours, or 2.5 hours, or 3 hours, or 3.5 hours, or 4 hours, or 4.5 hours, or 5 hours, or 5.5 hours, or 6 hours, or 6.5 hours, or 7 hours, or 7.5 hours, or 8 hours.

[0088] According to one embodiment, sub-step a-2) is performed for 3 to 8 hours, or 4 to 6 hours.

[0089] dry

[0090] According to a preferred embodiment, in the catalyst of the first aspect of the present application, step a) further comprises: after sub-step a-1) and before sub-step a-2), cooling the mixture obtained in sub-step a-1) to room temperature and drying.

[0091] According to a preferred embodiment, the drying is spray drying. According to a preferred embodiment, the drying is carried out in a drying tower. However, it is known to those skilled in the art that the mixture in sub-step a-1) can also be dried using a method other than a drying tower in order to carry out the subsequent sub-step a-2), provided that the dried mixture obtained by the method used is suitable for the process in sub-step a-2).

[0092] According to a non-limiting embodiment, the drying tower comprises at least one inlet and at least one outlet, at least one of the inlets of the drying tower is configured to receive the mixture from sub-step a-1), and at least one of the outlets of the drying tower is configured to receive the dried mixture from sub-step a-1).

[0093] According to a non-limiting embodiment, the temperature of the drying tower is 150 to 300° C., or 150 to 250° C., or 200 to 250° C., or 220 to 240° C. For example, the temperature of the drying tower is 150° C., or 155° C., or 160° C., or 165° C., or 170° C., or 175° C., or 180° C., or 185° C., or 190° C., or 195° C., or 200° C., or 205° C., or 210° C., or 215° C., or 220° C., or 225° C., or 230° C., or 235° C., or 240° C., or 245° C., or 250° C., or 255° C., or 260° C., or 265° C., or 270° C., or 275° C., or 280° C., or 285° C., or 290° C., or 295° C., or 300° C.

[0094] According to a non-limiting embodiment, the outlet temperature of the drying tower is 100 to 250° C., or 140 to 200° C., or 160 to 180° C. For example, the outlet temperature of the drying tower may be 100° C., or 105° C., or 110° C., or 115° C., or 120° C., or 125° C., or 130° C., or 135° C., or 140° C., or 145° C., or 150° C., or 155° C., or 160° C., or 165° C., or 170° C., or 175° C., or 180° C., or 185° C., or 190° C., or 195° C., or 200° C., or 205° C., or 210° C., or 215° C., or 220° C., or 225° C., or 230° C., or 235° C., or 240° C., or 245° C., or 250° C.

[0095] Step b)

[0096] In the catalyst of the first aspect of the present application, step b) involves treating the carrier obtained in a) with a surfactant to obtain the modified carrier.

[0097] [Surfactant]

[0098] In an embodiment of the present application, the surfactant is selected from one or more of organic ammonium salts, organic carboxylates, organic sulfonates, and polymer surfactants.

[0099] In a preferred embodiment, the surfactant is selected from organic ammonium salts.

[0100] <Organic ammonium salt>

[0101] According to one embodiment, N of the organic ammonium salt is substituted by 1 to 4 (e.g., 1, 2, 3, 4) of the following groups:

[0102] -C1 to C 18 Hydrocarbyl, such as C1 to C 18 Alkyl, C2 to C 18 Alkenyl, C2 to C 18 Alkynyl;

[0103] -C5 to C 18 Alicyclic groups such as cyclopentyl, cyclohexyl, cyclooctyl, bicyclooctyl, cyclononyl, bicyclononyl, cyclodecyl, bicyclodecyl, and C1 to C 12 Alkyl, C2 to C 12 Alkenyl, C2 to C 12 Alkynyl-substituted cyclopentyl, cyclohexyl, cyclooctyl, bicyclooctyl, cyclononyl, bicyclononyl, cyclodecyl, bicyclodecyl;

[0104] -C5 to C 18 Aryl, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and C1 to C 12 Alkyl, C2 to C 12 Alkenyl, C2 to C 12 Alkynyl-substituted phenyl, naphthyl, anthracenyl, phenanthryl;

[0105] -C5 to C 18 Alkaryl, such as benzyl, and C1 to C 12 Alkyl, C2 to C 12 Alkenyl, C2 to C 12 Alkynyl substituted benzyl; or

[0106] -C5 to C 18 Aralkyl.

[0107] As C1 to C 18As examples of the alkyl group, there may be mentioned methyl, ethyl, n-propyl, n-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, palmityl, stearyl, isopropyl, isobutyl, tert-butyl, sec-butyl, 1-methylpropyl, 1-ethylpropyl, isopentyl, neopentyl, 1-methylbutyl, 3-methylbutyl, isohexyl, 1-methylpentyl, 3-methylpentyl, 1,1-dimethylpentyl, n-hexyl, 1-methylhexyl, 1-pentylhexyl and the like;

[0108] As C2 to C 18 As examples of alkenyl groups, there may be mentioned: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, linoleyl, oleyl;

[0109] As C2 to C 18 As examples of the alkynyl group, there may be mentioned ethynyl, propynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl.

[0110] The group on N of the organic ammonium salt may be optionally substituted by halogen, hydroxyl, alkoxy, mercapto, or alkylthio, or the group on N of the organic ammonium salt may be optionally substituted by oxo or thio.

[0111] According to one embodiment, the anion in the organic ammonium salt is selected from one or more of the following:

[0112] - halides, for example fluoride, chloride, bromide;

[0113] - inorganic acid radicals, such as nitrate, phosphate, carbonate, bicarbonate;

[0114] - Organic acid radicals, such as acetate, propionate, butyrate, oxalate.

[0115] <Sulfonate>

[0116] According to one embodiment, the surfactant is selected from sulfonates. According to one embodiment, the sulfonate is C4-C 16 Sulfonate.

[0117] According to one embodiment, the sulfonate is selected from alkyl sulfonates.

[0118] As examples of alkyl sulfonates, mention may be made of: butanesulfonate, pentanesulfonate, hexanesulfonate, heptanesulfonate, octanesulfonate, nonanesulfonate, decanesulfonate, undecanesulfonate, dodecanesulfonate, tridecanesulfonate, tetradecanesulfonate, pentadecanesulfonate, hexadecanesulfonate. Optionally, the alkyl group in the alkyl sulfonate may be substituted with halogen, hydroxyl, alkoxy, mercapto, alkylthio, or the alkyl group in the alkyl sulfonate may be oxo- or thio-substituted.

[0119] According to one embodiment, the sulfonate is selected from aromatic sulfonates. As non-limiting examples, mention may be made of: benzene sulfonate, methylbenzene sulfonate, ethylbenzene sulfonate, propylbenzene sulfonate, butylbenzene sulfonate, pentylbenzene sulfonate, hexylbenzene sulfonate, heptylbenzene sulfonate, octylbenzene sulfonate, nonylbenzene sulfonate, decylbenzene sulfonate. Optionally, the group in the aromatic sulfonate may be substituted by halogen, hydroxyl, alkoxy, sulfhydryl, alkylthio, or the group in the alkyl sulfonate may be oxo or thio.

[0120] According to one embodiment, the sulfonate is an ammonium salt.

[0121] <Organic carboxylates>

[0122] According to one embodiment, the surfactant is selected from organic carboxylates. According to one embodiment, the organic carboxylates are selected from C5-C 18 Aliphatic carboxylic acids, C5-C 18 Salt of alicyclic carboxylic acid According to an exemplary embodiment, the surfactant may be stearate, palmitate, oleate, linoleate, cyclohexanedicarboxylate, or dicyclodecanedicarboxylate.

[0123] According to one embodiment, the organic acid salt is an ammonium salt of an organic acid.

[0124] <Polymer surfactant>

[0125] According to one embodiment, the surfactant is selected from polymeric surfactants. In one embodiment, the polymeric surfactant is selected from PEG, PTMG, polymethacrylate or polyacrylamide.

[0126] According to an exemplary but non-limiting embodiment, the surfactant is selected from: one or more of hexadecyltrimethylammonium bromide, short-chain polyacrylamide, tetramethylammonium bromide, butyltrimethylammonium bromide, octyltrimethylammonium bromide, and dodecyltrimethylammonium bromide.

[0127] The mass ratio of the surfactant to the carrier depends on the desired catalyst properties. According to one embodiment of the present application, in the modified carrier described in the first aspect of the present application, the mass ratio of the surfactant to the carrier is 0.05 to 0.8, or 0.1 to 0.5, or 0.15 to 0.3. For example, in the catalyst described in the first aspect of the present application, the mass ratio of the surfactant to the carrier may be 0.05, or 0.06, or 0.08, or 0.10, or 0.11, or 0.12, or 0.13, or 0.14, or 0.15, or 0.16, or 0.17, or 0.18, or 0.19, or 0.20, or 0.21, or 0.22, or 0.23, or 0.24, or 0.25, or 0.26, or 0.27, or 0.28. 28, or 0.29, or 0.30, or 0.32, or 0.34, or 0.36, or 0.38, or 0.40, or 0.42, or 0.44, or 0.46, or 0.48, or 0.50, or 0.52, or 0.54, or 0.56, or 0.58, or 0.60, or 0.62, or 0.64, or 0.66, or 0.68, or 0.70, or 0.72, or 0.74, or 0.76, or 0.78, or 0.80.

[0128] Step b) can be carried out in a manner well known to those skilled in the art.

[0129] According to one embodiment, step b) is carried out in a composite solvent of water and an organic solvent. According to one embodiment, the organic solvent is:

[0130] - saturated or unsaturated, linear or branched, cyclic or acyclic C1 to C 18 Alcohols, such as methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanediol, ethylene glycol, propylene glycol, butanediol;

[0131] - saturated or unsaturated, linear or branched, cyclic or acyclic C3 to C 18 Ketones, for example acetone, butanone, cyclohexanone, benzophenone, acetophenone.

[0132] According to one embodiment, in the composite solvent, the mass ratio of water:organic solvent is 1 to 20, more preferably 2 to 10, and most preferably 3 to 6.

[0133] According to one embodiment, step b) lasts from 0.1 to 8 h, or from 0.2 to 4 h, or from 0.5 to 2 h. According to an exemplary embodiment, the duration of step b) may be 0.1 h, or 0.2 h, or 0.3 h, or 0.4 h, or 0.5 h, or 0.6 h, or 0.7 h, or 0.8 h, or 0.9 h, or 1.0 h, or 1.1 h, or 1.2 h, or 1.3 h, or 1.4 h, or 1.5 h, or 1.6 h, or 1.7 h, or 1.8 h, or 1.9 h, or 2.0 h, or 2.2 h, or 2.4 h, or 2.6 h, or 2.8 h, or 3.0 h, or 3.2 h, or 3.4 h, or 3.6 h, or 3.8 h, or 4.0 h, or 4.5 h, or 5.0 h, or 5.5 h, or 6.0 h, or 6.5 h, or 7.0 h, or 7.5 h, or 8.0 h.

[0134] According to one embodiment, step b) is carried out at a temperature of 40 to 120° C., or 40 to 80° C., or 40 to 60° C. According to an exemplary embodiment, step b) is carried out at a temperature of 40° C., or 42° C., or 44° C., or 46° C., or 48° C., or 50° C., or 52° C., or 54° C., or 56° C., or 58° C., or 60° C., or 62° C., or 64° C., or 66° C., or 68° C., or 70° C., or 75° C., or 80° C., or 85° C., or 90° C., or 95° C., or 100° C., or 105° C., or 110° C., or 115° C., or 120° C.

[0135] Method for preparing modified carrier

[0136] The second aspect of the present application relates to a method for preparing the modified carrier described in the first aspect of the present application, the method comprising the following steps:

[0137] a) preparing a carrier using a composition comprising a metal source and a silicon source;

[0138] b) treating the carrier in step a) with a surfactant to form the modified carrier;

[0139] The surfactant is selected from one or more of organic ammonium salts, organic carboxylates, organic sulfonates and polymer surfactants.

[0140] According to a preferred embodiment, step a) of the method of the second aspect of the present application comprises the following sub-steps:

[0141] a-1) mixing a first solution comprising the metal source and optionally an acid and a second solution comprising a silicon source to obtain a mixture;

[0142] a-2) calcining the mixture from sub-step a-1).

[0143] The various steps described in the second aspect of the present application as well as the metal source, silicon source, and surfactant are the same as those described in the first aspect of the present application.

[0144] catalyst

[0145] The third aspect of the present application relates to a catalyst, which is prepared by the following steps:

[0146] i) supporting a catalyst active component precursor on the modified carrier as described in the first aspect of the present application; and

[0147] ii) subjecting the product of step i) to calcination.

[0148] Step i)

[0149] [Active ingredient precursor]

[0150] According to one embodiment, the active component precursor comprises a soluble metal salt or a metal complex, wherein the metal in the catalyst active component precursor is selected from transition metals.

[0151] According to a preferred embodiment, the metal in the catalyst active component precursor is selected from copper, silver, gold, zinc, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, lanthanum, cerium, and erbium.

[0152] According to a preferred embodiment, the metal in the catalyst active component precursor is selected from copper.

[0153] According to one embodiment, the active component precursor is selected from one or more of the following: chlorides, nitrates, sulfates, hydrogen sulfates, phosphates, hydrogen phosphates, dihydrogen phosphates of metals; and complexes of metals with OH and Cl.

[0154] According to a non-limiting embodiment, the active component precursor is copper nitrate and / or copper nitrate hydrate.

[0155] The mass ratio of the catalyst active component precursor to the carrier may be adjusted according to the desired catalyst properties.

[0156] According to one embodiment, the mass ratio of the catalyst active component precursor to the carrier is 2.0 to 10.0, or 2.2 to 9.8, or 2.4 to 9.6, or 2.6 to 9.4, or 2.8 to 9.2, or 3.0 to 9.0, or 3.2 to 8.8, or 3.4 to 8.6, based on the dry weight of the catalyst active component precursor and the dry weight of the carrier.

[0157] For example, the mass ratio of the catalyst active component precursor to the carrier may be 2.0, or 2.2, or 2.4, or 2.6, or 2.8, or 3.0, or 3.2, or 3.4, or 3.6, or 3.8, or 4.0, or 4.2, or 4.4, or 4.6, or 4.8, or 5.0, or 5.2, or 5.4, or 5.6, or 5.8, or 6.0, or 6.2, or 6.4, or 6.6, or 6.8, or 7.0, or 7.2, or 7.4, or 7.6, or 7.8, or 8.0, or 8.2, or 8.4, or 8.6, or 8.8, or 9.0, or 9.2, or 9.4, or 9.6, or 9.8, or 10, based on the dry weight of the catalyst active component precursor and the dry weight of the carrier.

[0158] [Precipitant]

[0159] According to one embodiment, the precipitant is selected from one or more of the following: hydroxide, chloride, carbonate, bicarbonate, sulfate, bisulfate, phosphate, hydrogen phosphate, or dihydrogen phosphate of a metal.

[0160] According to a preferred embodiment, the precipitant is selected from carbonates and / or hydroxides of metals.

[0161] The metal in the precipitant is not particularly limited. According to a preferred embodiment, the metal in the precipitant is selected from alkali metals or alkaline earth metals, such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, and strontium.

[0162] As non-limiting examples of the precipitating agent, mention may be made of sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, or potassium hydroxide.

[0163] The mass ratio of the precipitant to the active component precursor can be adjusted according to the active component precursor and precipitant specifically used.

[0164] According to a non-limiting embodiment, the mass ratio of the precipitant to the active component precursor is 0.1 to 4, or 0.15 to 3, or 0.2 to 2, or 0.25 to 1.8, or 0.30 to 1.6, or 0.35 to 1.4, or 0.40 to 1.2, based on the dry weight of the precipitant and the active component precursor.

[0165] According to one embodiment, the mass ratio of the precipitant to the active component precursor is 0.1, or 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or 1.0, or 1.1, or 1.2, or 1.3, or 1.4, or 1.5, or 1.6, or 1.7, or 1.8, or 1.9, or 2.0, or 2.1, or 2.2, or 2.3, or 2.4, or 2.5, or 2.6, or 2.7, or 2.8, or 2.9, or 3.0, or 3.1, or 3.2, or 3.3, or 3.4, or 3.5, or 3.6, or 3.7, or 3.8, or 3.9, or 4.0, based on the dry weight of the precipitant and the active component precursor.

[0166] According to one embodiment, the mass ratio of the precipitant to the active component precursor is 0.1, or 0.12, or 0.14, or 0.16, or 0.18, or 0.20, or 0.22, or 0.24, or 0.26, or 0.28, or 0.30, or 0.32, or 0.34, or 0.36, or 0.38, or 0.40, or 0.42, or 0.44, or 0.46, or 0.48, or 0.50, or 0.52, or 0.5 4, or 0.56, or 0.58, or 0.60, or 0.62, or 0.64, or 0.66, or 0.68, or 0.70, or 0.72, or 0.74, or 0.76, or 0.78, or 0.80, or 0.82, or 0.84, or 0.86, or 0.88, or 0.90, or 0.92, or 0.94, or 0.96, or 0.98, or 1.00, based on the dry weight of the precipitant and the active ingredient precursor.

[0167] [Auxiliary agent precursor]

[0168] According to one embodiment, step i) involves loading a catalyst active component precursor and a promoter precursor on the modified carrier as described in the first aspect of the present application.

[0169] The transition metal in the additive precursor is selected from one or more of zinc, zirconium, molybdenum, titanium, gold, cobalt, lanthanum, or cerium.

[0170] The mass ratio of the promoter precursor to the carrier can be adjusted according to the desired catalyst properties and the specific promoter precursor.

[0171] According to a non-limiting embodiment, the mass ratio of the auxiliary agent precursor to the carrier is 0.20 to 4.0, or 0.25 to 3.5, or 0.30 to 3.0, or 0.35 to 2.5, based on the dry weight of the auxiliary agent precursor and the carrier. For example, the mass ratio of the auxiliary agent precursor to the carrier can be 0.20, or 0.25, or 0.30, or 0.35, or 0.40, or 0.45, or 0.50, or 0.55, or 0.60, or 0.65, or 0.70, or 0.75, or 0.80, or 0.85, or 0.90, or 0.95, or 1.00, or 1.05, or 1.10, or 1.15, or 1.20, or 1.25, or 1.30, or 1.35, or 1.40, or 1.45, or 1.50, or 1.55, or 1.60, or 1.65, or 1.70, or 1.75, or 1.80, or 1.85, or 1.90, or 1.95, or 2.00, or 2.05, or 2. 10, or 2.15, or 2.20, or 2.25, or 2.30, or 2.35, or 2.40, or 2.45, or 2.50, or 2.55, or 2.60, or 2.65, or 2.70, or 2.75, or 2.80, or 2.85, or 2.90, or 2.95, or 3.00, or 3.05, or 3.10, or 3 .15, or 3.20, or 3.25, or 3.30, or 3.35, or 3.40, or 3.45, or 3.50, or 3.55, or 3.60, or 3.65, or 3.70, or 3.75, or 3.80, or 3.85, or 3.90, or 3.95, or 4.00, based on the dry weight of the adjuvant precursor and the carrier.

[0172] The mass ratio of the precipitant to the auxiliary agent precursor can be adjusted according to the specific precipitant and auxiliary agent precursor used.

[0173] According to a non-limiting embodiment, the mass ratio of the precipitant to the auxiliary agent precursor is 0.1 to 10, or 0.2 to 9.5, or 0.3 to 9.0, or 0.4 to 8.5, or 0.5 to 8.0, or 0.6 to 7.5, or 0.7 to 7.0, or 0.8 to 6.5, based on the dry weight of the precipitant and the auxiliary agent precursor. For example, the mass ratio of the precipitant to the auxiliary agent precursor may be 0.1, or 0.2, or 0.3, or 0.4, or 0.5, or 0.6, or 0.7, or 0.8, or 0.9, or 1.0, or 1.1, or 1.2, or 1.3, or 1.4, or 1.5, or 1.6, or 1.7, or 1.8, or 1.9, or 2.0, or 2.1, or 2.2, or 2.3, or 2.4, or 2.5, or 2.6, or 2.7, or 2.8, or 2.9, or 3.0, or 3.1, or 3.2, or 3.3, or 3.4, or 3.5, or 3.6, or 3.7, or 3.8, or 3.9, or 4.0, or 4.1, or 4.2, or 4.3, or 4.4, or 4.5, or 4.6, or 4.7, or 4.8, or 4.9, or 5.0, or 5.1, or 5.2, or 5.3, or 5.4, or 5.5, or 5.6, or 5.7, or 5.8, or 5.9, or 6.0, or 6.1, or 6.2, or 6.3, or 6.4, or 6.5, or 6.6, or 6.7, or 6.8, or 6.9, or 7.0, or 7.1, or 7.2, or 7.3, or 7.4, or 7.5, or 7.6, or 7.7, or 7.8, or 7.9, or 8.0, or 8.1, or 8.2, or 8.3, or 8.4, or 8.5, or 8.6, or 8.7, or 8.8, or 8.9, or 9.0, or 9.1, or 9.2, or 9.3, or 9.4, or 9.5, or 9.6, or 9.7, or 9.8, or 9.9, or 10.0, based on the dry weight of the precipitant and the adjuvant precursor.

[0174] According to a preferred embodiment, step i) comprises the following sub-steps:

[0175] i-1) preparing the following third solution and fourth solution, wherein the third solution comprises the catalyst active component precursor and optionally the promoter precursor; the fourth solution comprises the precipitant;

[0176] i-2) adding the third solution and the fourth solution in parallel to the modified support as described in the first aspect of the present application.

[0177] Sub-step i-1)

[0178] [Third solution]

[0179] In the third solution, the concentration of the auxiliary agent precursor is adjusted according to the specific auxiliary agent precursor.

[0180] According to an exemplary embodiment, in the third solution, the concentration of the auxiliary agent precursor is 0.2 to 3 mol / L, or 0.5 to 1.5 mol / L, or 1 to 1.5 mol / L.

[0181] For example, in the third solution, the concentration of the auxiliary agent precursor may be 0.1 mol / L, or 0.2 mol / L, or 0.3 mol / L, or 0.4 mol / L, or 0.5 mol / L, or 0.6 mol / L, or 0.7 mol / L, or 0.8 mol / L, or 0.9 mol / L, or 1.0 mol / L, or 1.1 mol / L, or 1.2 mol / L, or 1.3 mol / L, or 1.4 mol / L , or 1.5mol / L, or 1.6mol / L, or 1.7mol / L, or 1.8mol / L, or 1.9mol / L, or 2.0mol / L, or 2.1mol / L, or 2.2mol / L, or 2.3mol / L, or 2.4mol / L, or 2.5mol / L, or 2.6mol / L, or 2.7mol / L, or 2.8mol / L, or 2.9mol / L, or 3.0mol / L.

[0182] [Fourth solution]

[0183] In the fourth solution, the concentration of the precipitant depends on the specific precipitant species used.

[0184] According to a non-limiting embodiment, the concentration of the precipitant in the fourth solution is 0.3 to 3 mol / L, or 0.8 to 2 mol / L, or 1 to 1.8 mol / L.

[0185] For example, the concentration of the precipitant in the fourth solution may be 0.3mol / L, or 0.4mol / L, or 0.5mol / L, or 0.6mol / L, or 0.7mol / L, or 0.8mol / L, or 0.9mol / L, or 1.0mol / L, or 1.1mol / L, or 1.2mol / L, or 1.3mol / L, or 1.4mol / L, or 1.5mol / L, or 1.6mol / L, or 1.7mol / L, or 1.8mol / L, or 1.9mol / L, or 2.0mol / L, or 2.1mol / L, or 2.2mol / L, or 2.3mol / L, or 2.4mol / L, or 2.5mol / L, or 2.6mol / L, or 2.7mol / L, or 2.8mol / L, or 2.9mol / L, or 3.0mol / L.

[0186] Sub-step i-2)

[0187] Sub-step i-2) involves adding the third solution and the fourth solution in parallel to the modified support described in the first aspect of the present application.

[0188] The flow rate after the parallel flow is 1 to 10 mL / min, or 2 to 8 mL / min, or 3 to 7 mL / min. For example, in sub-step c-3), the flow rate after the parallel flow can be 1 mL / min, or 1.2 mL / min, or 1.4 mL / min, or 1.6 mL / min, or 1.8 mL / min, or 2.0 mL / min, or 2.2 mL / min, or 2.4 mL / min, or 2.6 mL / min, or 2.8 mL / min, or 3.0 mL / min, or 3.2 mL / min, or 3.4 mL / min, or 3.6 mL / min, or 3.8 mL / min, or 4.0 mL / min, or 4.2 mL / min, or 4.4 mL / min, or 4.6 mL / min, or 4.8 mL / min, or 5.0 mL / min, or 5.2 mL / min, or 5. 4mL / min, or 5.6mL / min, or 5.8mL / min, or 6.0mL / min, or 6.2mL / min, or 6.4mL / min, or 6.6mL / min, or 6.8mL / min, or 7.0mL / min, or 7.2mL / min, or 7.4mL / min, or 7.6mL / min, or 7.8mL / min, or 8.0mL / min, or 8.2mL / min, or 8.4mL / min, or 8.6mL / min, or 8.8mL / min, or 9.0mL / min, or 9.2mL / min, or 9.4mL / min, or 9.6mL / min, or 9.8mL / min, or 10.0mL / min.

[0189] According to one embodiment, step i) may be performed at a pH of 7 to 11, or 8 to 10, or 8 to 9.

[0190] For example, according to one non-limiting embodiment, step i) is carried out at a pH of 7.0, or 7.1, or 7.2, or 7.3, or 7.4, or 7.5, or 7.6, or 7.7, or 7.8, or 7.9, or 8.0, or 8.1, or 8.2, or 8.3, or 8.4, or 8.5, or 8.6, or 8.7, or 8.8, or 8.9, or 9.0, or 9.1, or 9.2, or 9.3, or 9.4, or 9.5, or 9.6, or 9.7, or 9.8, or 9.9, or 10.0, or 10.1, or 10.2, or 10.3, or 10.4, or 10.5, or 10.6, or 10.7, or 10.8, or 10.9, or 11.0.

[0191] According to one embodiment, step i) is performed under stirring. According to one embodiment, step i) is performed at a stirring speed of 100 to 500 rpm, or 150 to 400 rpm, or 250 to 350 rpm.

[0192] According to an exemplary embodiment, step i) of the method of the second aspect of the present application is at 100 rpm, or 110 rpm, or 120 rpm, or 130 rpm, or 140 rpm, or 150 rpm, or 160 rpm, or 170 rpm, or 180 rpm, or 190 rpm, or 200 rpm, or 210 rpm, or 220 rpm, or 230 rpm, or 240 rpm, or 250 rpm, or 260 rpm, or 270 rpm, or 280 rpm, or 290 rpm. The stirring is carried out at a stirring speed of 90 rpm, or 300 rpm, or 310 rpm, or 320 rpm, or 330 rpm, or 340 rpm, or 350 rpm, or 360 rpm, or 370 rpm, or 380 rpm, or 390 rpm, or 400 rpm, or 410 rpm, or 420 rpm, or 430 rpm, or 440 rpm, or 450 rpm, or 460 rpm, or 470 rpm, or 480 rpm, or 490 rpm, or 500 rpm.

[0193] Step ii)

[0194] Step ii) involves subjecting the product of step i) to calcination.

[0195] The calcination temperature in step ii) can be selected according to the modified support, active component precursor, optional auxiliary agent precursor, and precipitant actually used.

[0196] According to one embodiment, step ii) is carried out at a temperature of 200 to 700° C., or 250 to 500° C., or 300 to 400° C. For example, step ii) may be carried out at 200° C., or 210° C., or 220° C., or 230° C., or 240° C., or 250° C., or 260° C., or 270° C., or 280° C., or 290° C., or 300° C., or 310° C., or 320° C., or 330° C., or 340° C., or 350° C., or 360° C., or 370° C., or 380° C., or 390° C., or 400° C., or 410° C., or 420° C., or 430° C., or 440° C., or The quenching reaction is carried out at a temperature of 450°C, or 460°C, or 470°C, or 480°C, or 490°C, or 500°C, or 510°C, or 520°C, or 530°C, or 540°C, or 550°C, or 560°C, or 570°C, or 580°C, or 590°C, or 600°C, or 610°C, or 620°C, or 630°C, or 640°C, or 650°C, or 660°C, or 670°C, or 680°C, or 690°C, or 700°C.

[0197] The calcination time of step ii) can be selected according to the carrier, modified carrier, active component precursor, optional auxiliary agent precursor, surfactant, and precipitant actually used.

[0198] According to a non-limiting embodiment, step ii) is carried out for 1 to 12 hours, or 3 to 8 hours, or 4 to 6 hours. For example, step ii) is carried out for 1 hour, or 2 hours, or 3 hours, or 4 hours, or 5 hours, or 6 hours, or 7 hours, or 8 hours, or 9 hours, or 10 hours, or 11 hours, or 12 hours.

[0199] Method for preparing catalyst

[0200] In a fourth aspect, the present application relates to a method for producing the catalyst as described in the third aspect of the present application, the method comprising the following steps:

[0201] i) supporting a catalyst active component precursor and an optional auxiliary agent precursor on the modified carrier as described in the first aspect of the present application; and

[0202] ii) subjecting the product of step i) to calcination.

[0203] In a preferred embodiment, step i) comprises the following sub-steps:

[0204] i-1) preparing the following third solution and fourth solution, wherein the third solution comprises the catalyst active component precursor and optionally the promoter precursor; the fourth solution comprises the precipitant;

[0205] i-2) adding the third solution and the fourth solution in parallel to the modified support as described in the first aspect of the present application.

[0206] In the method described in the fourth aspect of the present application, the catalyst active component precursor, precipitant, auxiliary agent precursor, and each step are as described in the first to third aspects of the present application.

[0207] use

[0208] The fifth aspect of the present application relates to a method for producing methanol by hydrogenating CO2, which method uses the catalyst described in the third aspect of the present application.

[0209] The sixth aspect of the present application relates to the use of the catalyst described in the third aspect of the present application in a process for producing methanol by hydrogenation of carbon dioxide.

[0210] According to one embodiment, the process for producing methanol by hydrogenation of carbon dioxide is carried out at a temperature of 150 to 200° C., or 160 to 200° C., or 170 to 200° C., or 180 to 200° C. For example, the process for producing methanol by hydrogenation of carbon dioxide can be carried out at a temperature of 150° C., or 155° C., or 160° C., or 165° C., or 170° C., or 175° C., or 180° C., or 185° C., or 190° C., or 195° C., or 200° C.

[0211] According to one embodiment, the carbon dioxide hydrogenation methanol process is carried out at a pressure of 1 to 5 MPa, or 2 to 4 MPa. For example, the carbon dioxide hydrogenation methanol process can be carried out at a pressure of 1 MPa, or 1.2 MPa, or 1.4 MPa, or 1.6 MPa, or 1.8 MPa, or 2.0 MPa, or 2.2 MPa, or 2.4 MPa, or 2.6 MPa, or 2.8 MPa, or 3.0 MPa, or 3.2 MPa, or 3.4 MPa, or 3.6 MPa, or 3.8 MPa, or 4.0 MPa, or 4.2 MPa, or 4.4 MPa, or 4.6 MPa, or 4.8 MPa, or 5.0 MPa.

[0212] According to one embodiment, the carbon dioxide hydrogenation process for producing methanol is carried out at 2000-6000h -1 For example, the process for producing methanol by hydrogenation of carbon dioxide can be carried out at a space velocity of 2000 h. -1 , or 2500h -1 , or 3000h -1 , or 3500h -1 , or 4000h -1 , or 4500h -1 , or 5000h -1 , or 5500h -1 , or 6000h-1 Carry out at an airspeed of .

[0213] According to one embodiment, in the process for producing methanol by hydrogenation of carbon dioxide, the molar ratio of H2:CO2 is 2 to 6. For example, in the process for producing methanol by hydrogenation of carbon dioxide, the molar ratio of H2:CO2 is 2, or 2.2, or 2.4, or 2.6, or 2.8, or 3.0, or 3.2, or 3.4, or 3.6, or 3.8, or 4.0, or 4.2, or 4.4, or 4.6, or 4.8, or 5.0, or 5.2, or 5.4, or 5.6, or 5.8, or 6.0.

[0214] Example

[0215] The present invention will be further described below in conjunction with specific examples. It should be understood that the examples are provided for illustrative purposes only. The examples do not limit the scope of protection of the present application in any way.

[0216] The reagents and equipment used in the examples of this application are as follows:

[0217] Metal source

[0218] -Al(NO3)3·9H2O: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0219] -Mg(NO3)2·6H2O: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0220] -Ca(NO3)2·4H2O: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0221] Silicon source

[0222] - Silica sol: Jiangsu Xianfeng Nanomaterials Technology Co., Ltd., Xianfeng Nano #102587

[0223] acid

[0224] -Nitric acid: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0225] Active ingredient precursor

[0226] -Cu(NO3)2·3H2O: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0227] Precursor

[0228] -TiO2: Sinopharm Chemical Reagent Co., Ltd., CP (Shanghai trial)

[0229] -Zn(NO3)2·6H2O: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0230] -Zr(NO3)4·5H2O: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0231] Surfactants

[0232] - Hexadecyltrimethylammonium bromide (CTAB): Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0233] -Short-chain polyacrylamide: Sinopharm Chemical Reagent Co., Ltd., anion adsorbent (Shanghai trial)

[0234] - Dodecyltrimethylammonium bromide: Sinopharm Chemical Reagent Co., Ltd., 99% (Shanghai test)

[0235] Organic solvents

[0236] -Ethanol: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0237] -Methanol: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0238] -Acetone: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0239] Precipitating agent:

[0240] -Sodium carbonate: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0241] -Potassium carbonate: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0242] -Sodium bicarbonate: Sinopharm Chemical Reagent Co., Ltd., AR (Shanghai trial)

[0243] Example 1

[0244] The catalyst described in Example 1 is carried out by the following steps:

[0245] 1) Add 7.1g Al(NO3)3.9H2O, 4.8g Mg(NO3)2.6H2O and 0.24g HNO3 with a mass concentration of 60% to 8mL deionized water and stir evenly; slowly drop the above solution into 40g silica sol with a mass concentration of 30% at 50°C, and control the dropping time to 0.5h; continue to stir the mixed solution in a 50°C water bath for 24h to obtain a milky white transparent solution. The above solution is cooled to room temperature under stirring and spray dried to obtain a crude product. The spray drying conditions are: drying tower temperature 230°C, outlet temperature 170°C, to obtain a crude product. Then, the crude product is placed in an oven at 120°C and dried for 12h. Finally, the crude product is placed in a muffle furnace and calcined to obtain a carrier. The calcination conditions are: heating from 20 to 350°C for 2h, and maintaining at 350°C for 3h.

[0246] 2) Take 1.5g of hexadecyltrimethylammonium bromide (CTAB) and dissolve it in 100g of ethanol-water mixed solvent (water:ethanol=4:1, mass ratio), add 10g of the carrier obtained in step 1) to the solution, stir evenly, and react at 50°C for 0.5h.

[0247] 3) Take 36g of copper nitrate trihydrate and 15g of zinc nitrate hexahydrate and dissolve them in deionized water to prepare 200mL of mixed solution A with a concentration of 1mol / L, and take 23g of sodium carbonate and dissolve them in deionized water to prepare 200mL of solution B with a concentration of 1.1mol / L. Heat to 75°C, and add solutions A and B to the modified carrier obtained in step 2) at a flow rate of 6mL / min. Use mechanical stirring at a stirring rate of 300rpm, and keep the pH value of the solution at about 8.0 during the reaction. After the addition of solutions A and B, continue stirring for 3h, then stand at 30°C for 12h, wash and filter the slurry, and dry the precipitate at 110°C for 12h. Roast at 350°C for 5h, cool and tablet, and obtain catalyst a.

[0248] The obtained catalyst was characterized by XRD analysis. Figure 2 The results show obvious characteristic peaks of CuO and ZnO. The electron microscope image of the prepared catalyst is as follows Figure 3 As shown, the nanoparticles in the active center are distributed relatively evenly, with an average particle size of about 5.4 nm.

[0249] Example 2

[0250] Example 1 was repeated except that 21 g of zirconium nitrate pentahydrate was used to replace 15 g of zinc nitrate hexahydrate in Example 1. In Example 2, catalyst b was obtained.

[0251] Example 3

[0252] The catalyst in Example 3 was prepared by the following steps.

[0253] 1) Add 9g Al(NO3)3.9H2O, 5g Ca(NO3)2.4H2O and 0.3g 60% HNO3 to 10mL deionized water and stir evenly; slowly drop the above solution into 45g 30% silica sol aqueous solution at 60°C, and control the dropping time to 0.5h; continue to stir the mixed solution in a 60°C water bath for 20h to obtain a milky white transparent solution. The above solution is cooled to room temperature under stirring, and a crude product is obtained by drying, and the drying conditions are: drying at 120°C for 12h. Finally, the crude product is placed in a muffle furnace for calcination to obtain a carrier. The calcination conditions are: heating from 20 to 400°C for 2.5h, and maintaining at 400°C for 3h.

[0254] 2) Dissolve 2 g of short-chain polyacrylamide in 80 g of acetone-water mixed solvent (water:acetone=3:1, mass ratio), add 10 g of the carrier obtained in step 1) to the solution, stir evenly, and react at 50° C. for 1 h.

[0255] 3) Take 36g of copper nitrate trihydrate and 21g of zirconium nitrate pentahydrate and dissolve them in deionized water to prepare 200mL of mixed solution A with a concentration of 1mol / L, and take 28g of potassium carbonate and dissolve them in 200mL of deionized water to prepare solution B with a concentration of 1.1mol / L. Heat to 70°C, and add solutions A and B to the modified carrier obtained in step 2) at a flow rate of 4mL / min. Use mechanical stirring at a stirring rate of 250rpm, and keep the pH value of the solution at about 8.5 during the reaction. After the addition of solutions A and B, continue stirring for 4h, then stand at 30°C for 10h, wash and filter the slurry, and dry the precipitate at 120°C for 12h. Roast at 350°C for 6h, cool and tablet, and obtain catalyst c.

[0256] Example 4

[0257] The catalyst in Example 4 was prepared by the following steps.

[0258] 1) Add 6g Mg(NO3)2·4H2O and 0.25g 60% HNO3 to 15mL deionized water and stir evenly; slowly add the above solution to 30g 30% silica sol aqueous solution at 45°C, and the dropping time is controlled to 1h; continue to stir the mixed solution in a 45°C water bath for 22h to obtain a milky white transparent solution. The above solution is cooled to room temperature under stirring conditions, and a crude product is obtained by drying, and the drying conditions are: drying at 150°C for 12h. Finally, the crude product is placed in a muffle furnace and calcined to obtain a carrier. The calcination conditions are: heating from 20 to 350°C for 2h, and maintaining at 350°C for 3h.

[0259] 2) 1.8 g of dodecyltrimethylammonium bromide was dissolved in 85 g of a methanol-water mixed solvent (water:methanol=3.5:1, mass ratio), 8 g of the carrier obtained in step 1) was added to the solution, stirred evenly, and reacted at 60° C. for 1.5 h.

[0260] 3) Heat to 70°C, add 4g TiO2 to the modified carrier obtained in step 2), and stir evenly. Take 48g copper nitrate trihydrate and dissolve it in deionized water to prepare 200mL of mixed solution A with a concentration of 1mol / L, and take 24g sodium bicarbonate and dissolve it in deionized water to prepare 200mL of solution B with a concentration of 1.1mol / L. Add solutions A and B to the mixture containing TiO2 in parallel at a flow rate of 4mL / min. Use mechanical stirring at a stirring rate of 350rpm, and keep the pH value of the solution at about 9 during the reaction. After the addition of solutions A and B, continue stirring for 5h, then stand at 20°C for 10h, wash and filter the slurry, and dry the precipitate at 120°C for 12h. Roast at 400°C for 6h, cool down, and press into tablets to obtain catalyst d.

[0261] Example 5

[0262] The catalyst in Example 5 was prepared by the following steps.

[0263] 1) Add 6g Mg(NO3)2.4H2O and 0.25g 60% HNO3 to 15mL deionized water and stir evenly; slowly drop the above solution into 30g 30% silica sol aqueous solution at 45°C, and control the dropping time to 1h; continue to stir the mixed solution in a 45°C water bath for 22h to obtain a milky white transparent solution. Cool the above solution to room temperature under stirring, and obtain a crude product by spray drying. The spray drying conditions are: drying tower temperature 220°C, outlet temperature 160°C.

[0264] Next, the crude product was placed in an oven at 120° C. to dry for 12 h. Finally, the crude product was placed in a muffle furnace to calcine to obtain a support. The calcination conditions were: heating from 20 to 350° C. for 2 h, and maintaining at 350° C. for 3 h.

[0265] 2) 1.8 g of dodecyltrimethylammonium bromide was dissolved in 85 g of a methanol-water mixed solvent (water:methanol=3.5:1, mass ratio), 8 g of the carrier obtained in step 1) was added to the solution, stirred evenly, and reacted at 60° C. for 1.5 h.

[0266] 3) Take 60g of copper nitrate trihydrate and 15g of zinc nitrate pentahydrate in deionized water to prepare 200mL of mixed solution A with a concentration of 1.5mol / L, and take 36g of sodium carbonate and dissolve it in 200mL of deionized water to prepare solution B with a concentration of 1.7mol / L. Heat to 70°C, and add solutions A and B to the modified carrier obtained in step 2) at a flow rate of 5mL / min. Use mechanical stirring at a stirring rate of 300rpm, and keep the pH value of the solution at about 8.5 during the reaction. After the addition of solutions A and B, continue stirring for 4h, then stand at 30°C for 8h, wash and filter the slurry, and dry the precipitate at 120°C for 12h. Roast at 350°C for 6h, cool and tablet, and obtain catalyst e.

[0267] Example 6

[0268] Example 1 was repeated, except that the subsequent reaction temperature for hydrogenating carbon dioxide to produce methanol was 180° C. Catalyst f was obtained.

[0269] Example 7

[0270] Example 1 was repeated, except that 2 g of short-chain polyacrylamide dissolved in 80 g of acetone-water mixed solvent (water:acetone=3:1, mass ratio) was used in step 2) to obtain catalyst g.

[0271] Example 8

[0272] Example 1 was repeated, except that 1.27 g of dodecyltrimethylammonium bromide dissolved in 85 g of a methanol-water mixed solvent (water:methanol=3.5:1, mass ratio) was used in step 2) to obtain catalyst h.

[0273] Example 9

[0274] Example 1 was repeated, except that 5.6 g of Ca(NO3)2.4H2O was used instead of 4.8 g of Al(NO3)3.9H2O in step 1), and the mass of the silica sol was increased to 50.7 g to obtain catalyst k.

[0275] Comparative Example 1

[0276] The support was prepared in the same manner as in Example 1. The catalyst in Comparative Example 1 was prepared by the following steps:

[0277] 1) Add 7.1g Al(NO3)3.9H2O, 4.8g Mg(NO3)2.6H2O and 0.24g 60% HNO3 to 8mL deionized water and stir evenly; slowly drop the above solution into 40g 30% silica sol aqueous solution at 50°C, and control the dropping time to 0.5h; continue to stir the mixed solution in a 50°C water bath for 24h to obtain a milky white transparent solution. Cool the above solution to room temperature under stirring, and obtain a crude product by spray drying. The spray drying conditions are: drying tower temperature 230°C, outlet temperature 170°C.

[0278] Next, the crude product was placed in an oven at 120° C. to dry for 12 h. Finally, the crude product was placed in a muffle furnace to calcine to obtain a support. The calcination conditions were: heating from 20 to 350° C. for 2 h, and maintaining at 350° C. for 3 h.

[0279] 2) Take 36g of copper nitrate trihydrate and 15g of zinc nitrate hexahydrate and dissolve them in deionized water to prepare 200mL of mixed solution A with a concentration of 1mol / L, and take 23g of sodium carbonate and dissolve them in deionized water to prepare 200mL of solution B with a concentration of 1.1mol / L. Heat to 75°C, and add solutions A and B to the carrier obtained in step 1) at a flow rate of 6mL / min. Use mechanical stirring at a stirring rate of 300rpm, and keep the pH value of the solution at about 8.0 during the reaction. After the addition of solutions A and B, continue stirring for 3h, then stand at 30°C for 12h, wash and filter the slurry, and dry the precipitate at 110°C for 12h. Roast at 350°C for 5h, cool and tablet, and obtain reference catalyst a'.

[0280] Comparative Example 2

[0281] The support was prepared in the same manner as in Example 1. The catalyst in Comparative Example 2 was prepared by the following steps.

[0282] 1) Add 7.1g Al(NO3)3.9H2O, 4.8g Mg(NO3)2.6H2O and 0.24g 60% HNO3 to 8mL deionized water and stir evenly; slowly drop the above solution into 40g 30% silica sol aqueous solution at 50°C, and control the dropping time to 0.5h; continue to stir the mixed solution in a 50°C water bath for 24h to obtain a milky white transparent solution. Cool the above solution to room temperature under stirring and obtain a crude product by drying. The spray drying conditions are: drying tower temperature 230°C, outlet temperature 170°C.

[0283] Next, the crude product was placed in an oven at 120° C. to dry for 12 h. Finally, the crude product was placed in a muffle furnace to calcine to obtain a support. The calcination conditions were: heating from 20 to 350° C. for 2 h, and maintaining at 350° C. for 3 h.

[0284] 2) Take 36g of copper nitrate trihydrate and 21g of zirconium nitrate pentahydrate and dissolve them in deionized water to prepare 200mL of mixed solution A with a concentration of 1mol / L, and take 23g of sodium carbonate and dissolve them in 200mL of deionized water to prepare solution B with a concentration of 1.1mol / L. Heat to 75°C, and add solutions A and B to the carrier obtained in step 1) at a flow rate of 6mL / min. Use mechanical stirring at a stirring rate of 300rpm, and keep the pH value of the solution at about 8.0 during the reaction. After the addition of solutions A and B, continue stirring for 3h, then stand at 30°C for 12h, wash and filter the slurry, and dry the precipitate at 110°C for 12h. Roast at 350°C for 5h, cool and tablet, and obtain reference catalyst b'.

[0285] Comparative Example 3

[0286] The catalyst in Comparative Example 3 was prepared by the following steps.

[0287] 1) Take 1.5g of hexadecyltrimethylammonium bromide (CTAB) and dissolve it in 100g of ethanol-water mixed solvent (water: ethanol = 4:1, mass ratio); add 7.1g of Al(NO3)3.9H2O, 4.8g of Mg(NO3)2.6H2O and 0.24g of 60% HNO3 by mass concentration to 8mL of deionized water and stir evenly with the above solution; then slowly add it dropwise to 40g of 30% silica sol aqueous solution at 50°C, and the dropping time is controlled to 0.5h; continue to stir the mixed solution in a 50°C water bath for 24h to obtain a milky white transparent solution. The above solution is cooled to room temperature under stirring conditions, and a crude product is obtained by spray drying. The spray drying conditions are: drying tower temperature 230°C, outlet temperature 170°C.

[0288] Next, the crude product was placed in an oven at 120° C. and dried for 12 h. Finally, the crude product was placed in a muffle furnace and calcined to obtain a comparative support. The calcination conditions were: heating from 20 to 350° C. for 2 h, and maintaining at 350° C. for 3 h.

[0289] 2) Take 10g of the comparative carrier obtained in step 1); dissolve 36g of copper nitrate trihydrate and 15g of zinc nitrate hexahydrate in deionized water to prepare 200mL of mixed solution A with a concentration of 1mol / L, and dissolve 23g of sodium carbonate in deionized water to prepare 200mL of solution B with a concentration of 1.1mol / L. Heat to 75°C, and add solutions A and B to the comparative carrier obtained in step 1) in parallel, with a flow rate of 6mL / min. Mechanical stirring is adopted, and the stirring rate is 300rpm. The pH value of the solution is kept at about 8.0 during the reaction. After the addition of solutions A and B is completed, continue stirring for 3h, then stand at 30°C for 12h, wash and filter the slurry, and dry the precipitate at 110°C for 12h. Roast at 350°C for 5h, cool down, and press into tablets to obtain catalyst c'.

[0290] Comparative Example 4

[0291] The catalyst in Comparative Example 4 was prepared by the following steps:

[0292] 1) Add 14.2g Al(NO3)3.9H2O and 0.24g 60% HNO3 to 8mL deionized water and stir evenly; slowly drop the above solution into 40g 30% silica sol aqueous solution at 50°C, and control the dropping time to 0.5h; continue to stir the mixed solution in a 50°C water bath for 24h to obtain a milky white transparent solution. Cool the above solution to room temperature under stirring, and obtain a crude product by spray drying. The spray drying conditions are: drying tower temperature 230°C, outlet temperature 170°C.

[0293] Next, the crude product was placed in an oven at 120° C. and dried for 12 h. Finally, the crude product was placed in a muffle furnace and calcined to obtain a comparative support. The calcination conditions were: heating from 20 to 350° C. for 2 h, and maintaining at 350° C. for 3 h.

[0294] 2) Take 1.5g of hexadecyltrimethylammonium bromide (CTAB) and dissolve it in 100g of ethanol-water mixed solvent (water:ethanol=4:1, mass ratio), add 10g of the reference carrier obtained in step 1) to the solution, stir evenly, and react at 50°C for 0.5h.

[0295] 3) Take 36g of copper nitrate trihydrate and 15g of zinc nitrate hexahydrate and dissolve them in deionized water to prepare 200mL of mixed solution A with a concentration of 1mol / L, and take 23g of sodium carbonate and dissolve them in deionized water to prepare 200mL of solution B with a concentration of 1.1mol / L. Heat to 75°C, and add solutions A and B to the modified comparative carrier obtained in step 2) at a flow rate of 6mL / min. Mechanical stirring is adopted, and the stirring rate is 300rpm. The pH value of the solution is kept at about 8.0 during the reaction. After the addition of solutions A and B is completed, stirring is continued for 3h, and then standing at 30°C for 12h, the slurry is washed and filtered, and the precipitate is dried at 110°C for 12h. Roast at 350°C for 5h, cool down, and press into tablets to obtain comparative catalyst d'.

[0296] Comparative Example 5

[0297] Example 1 was repeated, except that 60 g of copper nitrate trihydrate was used in step 3) to obtain catalyst e'.

[0298] The reaction performances of the CO2 hydrogenation to methanol catalysts prepared under different preparation process conditions under the above different embodiments and comparative examples are shown in Table 1.

[0299] Experimental reaction conditions:

[0300] Temperature: 180°C (Example 6), 200°C (other examples and comparative examples);

[0301] Airspeed: 3000h -1 ;

[0302] Pressure: 3MPa;

[0303] H2:CO2 molar ratio: 3:1.

[0304] Table 1 Reaction performance of CO2 hydrogenation to methanol catalysts prepared under different preparation process conditions

[0305] catalyst <![CDATA[CO2 conversion rate / %]]> Methanol selectivity / % (Methanol + CO) total selectivity / % Example 1 a 20.4 65.2 99.6 Example 2 b 18.2 63.3 99.5 Example 3 c 15.3 60.1 99.5 Example 4 d 17.6 62.5 99.5 Example 5 e 15.7 65.4 99.6 Example 6 f 15.1 70.1 99.5 Example 7 g 18.1 62.2 99.5 Example 8 h 18.8 64.8 99.6 Example 9 k 13.4 56.7 99.3 Comparative Example 1 a’ 14.2 55.1 99.5 Comparative Example 2 b’ 15.3 58.5 99.5 Comparative Example 3 c’ 17.5 60.3 99.4 Comparative Example 4 d’ 13.6 59.2 99.3 Comparative Example 5 e’ 17.1 65.6 99.5

[0306] As can be seen from the results in Table 1, the use of the modified carrier-supported catalyst active components (and additives) described in the present application enables the preparation of a carbon dioxide hydrogenation to methanol catalyst that can achieve high CO2 conversion and methanol selectivity. And compared with the carrier that has not been modified with a surfactant, a significantly higher CO2 conversion and methanol selectivity can be achieved. Among the three surfactants used in the examples, the organic ammonium salt type surfactant can further improve the CO2 conversion and methanol selectivity compared to the polymer type surfactant (as can be seen in Examples 1, 7 and 8)

[0307] Secondly, the process flow of preparing the modified support also has a significant impact on the performance of the final catalyst. The comparison results of Example 1 and Comparative Example 3 show that compared with the one-step preparation and surfactant modification in Comparative Example 3, the method in which the modification step is performed after the catalyst support is prepared can achieve significantly higher CO2 conversion and methanol selectivity.

[0308] The results in Table 1 also show that the choice of metal in the catalyst support has an impact on the properties of the final catalyst. The results of Example 1 and Comparative Example 4 show that if the support only contains metals that can form amphoteric metal oxides (such as Al), the CO2 conversion rate and methanol selectivity that can be achieved by the final catalyst are significantly lower than those using a catalyst in which the support contains a metal that can form a basic metal oxide (for example, in Example 1, the support contains Al and Mg).

[0309] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A modified carrier prepared by the following steps: a) preparing a carrier using a composition comprising a metal source and a silicon source; b) treating the carrier in step a) with a surfactant to form the modified carrier; The surfactant is selected from one or more of organic ammonium salts, organic carboxylates, organic sulfonates, and polymer surfactants; Preferably, the method has one or more of the following features: 1) The metal source is selected from one or more metal salts of the following metals: alkali metals, alkaline earth metals, or transition metals; Preferably, the metal in the metal source is selected from metals capable of forming amphoteric metal oxides, such as aluminum, gallium, zinc, titanium, or zirconium; and / or Preferably, the metal in the metal source is selected from rare earth metals, such as lanthanum, cerium, erbium; and / or 2) The metal source is selected from metal acetates, phosphates, nitrates, and hydrochlorides; preferably, the metal source is selected from metal nitrates; and / or 3) The silicon source is selected from silicon dioxide, silica sol, and organosiloxane; and / or 4) the mass ratio of the silicon source to the metal source is 0.5 to 3.0, or 0.8 to 2.0, or 0.9 to 1.7, based on the dry weight of the silicon source and the dry weight of the metal source; and / or 5) The composition in step a) further comprises an acid; preferably, the acid is selected from an organic acid or an inorganic acid; preferably, the organic acid is selected from: acetic acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, citric acid; preferably, the inorganic acid is selected from: hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid.

2. The modified carrier according to claim 1, wherein step a) comprises the following sub-steps: a-1) mixing a first solution comprising the metal source and optionally an acid and a second solution comprising a silicon source to obtain a mixture; a-2) calcining the mixture in sub-step a-1); Preferably, step a) has one or more of the following characteristics: 1) The acid in sub-step a-1) is selected from an organic acid or an inorganic acid; preferably, the organic acid is selected from acetic acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, and citric acid; preferably, the inorganic acid is selected from hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid; and / or 2) Sub-step a-1) is carried out at a temperature of 30 to 120°C, or 30 to 70°C, or 40 to 60°C; and / or 3) Sub-step a-1) is performed by: dropping the first solution into the second solution, and continuing mixing for a time t1 after the dropping is completed; Preferably the first solution is added dropwise to the second solution for a period of 0.1 h to 8 h, or 0.2 to 4 h, or 0.5 to 2 h; and / or Preferably t1 is 1 to 48h, or 12 to 36h, or 20 to 28h; and / or 4) Sub-step a-2) is carried out by heating from room temperature to calcination temperature T1 over time t2, and maintaining at T1 for time t3; Preferably T1 is 200 to 700°C, or 250 to 500°C, or 300 to 400°C; and / or t2 is 1 to 4 hours, or 1.5 to 3 hours; and / or t3 is 2 to 8 hours, or 2 to 6 hours, or 2 to 4 hours; and / or 5) Step a) further comprises: After sub-step a-1) and before sub-step a-2), the mixture obtained in sub-step a-1) is cooled to room temperature and dried; Preferably the drying is spray drying; and / or Preferably, the drying is carried out in a drying tower; More preferably, the temperature in the drying tower is 150 to 300°C, or 150 to 250°C, or 200 to 250°C, or 220 to 240°C; and / or The outlet temperature of the drying tower is 100 to 250°C, or 140 to 200°C, or 160 to 180°C.

3. The modified carrier of claim 1, wherein the surfactant has one or more of the following characteristics: 1) The surfactant is selected from organic ammonium salts; Preferably, the N of the organic ammonium salt is substituted by 1 to 4 of the following groups: C1 to C 18 Hydrocarbon, C5 to C 18 Alicyclic groups, C5 to C 18 Aryl, C5 to C 18 Alkaryl, C5 to C 18 Aralkyl; and / or The anion in the organic ammonium salt is selected from one or more of the following: - halides, for example fluoride, chloride, bromide; - inorganic acid radicals, such as nitrate, phosphate, carbonate, bicarbonate; - organic acid radicals, such as acetate, propionate, butyrate, oxalate; and / or 2) The sulfonate is selected from C4-C 16 Sulfonates; Preferably the sulfonate is or ammonium salt; and / or 3) The organic carboxylate is selected from C5-C 18 Aliphatic, C5-C 18 Salts of alicyclic carboxylic acids; Preferably, the organic acid salt is selected from or ammonium salt; and / or 4) The polymer surfactant is selected from PEG, PTMG, polymethacrylate or polyacrylamide; More preferably, the surfactant is selected from one or more of hexadecyltrimethylammonium bromide, short-chain polyacrylamide, tetramethylammonium bromide, butyltrimethylammonium bromide, octyltrimethylammonium bromide, and dodecyltrimethylammonium bromide.

4. The modified carrier according to claim 1, wherein the modified carrier has one or more of the following characteristics: 1) The mass ratio of the surfactant to the carrier is 0.05 to 0.8, or 0.1 to 0.5, or 0.15 to 0.3; and / or 2) step b) is carried out in a composite solvent of water and an organic solvent; Preferably, the organic solvent is selected from C1 to C 18 Alcohol or C3 to C 18 One or more of ketones; and or preferably in the composite solvent, the mass ratio of water: organic solvent is 1 to 20, or 2 to 10, or 3 to 6; and / or 3) step b) lasts for 0.1 to 8 hours, or 0.2 to 4 hours, or 0.5 to 2 hours; and / or 4) Step b) is carried out at a temperature of 40 to 120°C, or 40 to 80°C, or 40 to 60°C.

5. A method for preparing a modified carrier according to any one of claims 1 to 4, comprising the steps of: a) preparing a carrier using a composition comprising a metal source and a silicon source; b) treating the carrier in step a) with a surfactant to form the modified carrier; The surfactant is selected from one or more of organic ammonium salts, organic carboxylates, organic sulfonates, and polymer surfactants; Preferably, step a) comprises the following sub-steps: a-1) mixing a first solution comprising the metal source and optionally an acid and a second solution comprising a silicon source to obtain a mixture; a-2) calcining the mixture from sub-step a-1).

6. A catalyst prepared by the following steps: i) supporting a catalyst active component precursor and an optional auxiliary agent precursor on the modified carrier according to any one of claims 1 to 4; and ii) subjecting the product of step i) to calcination; Preferably, the catalyst has one or more of the following characteristics: 1) The catalyst active component precursor comprises a soluble metal salt or a metal complex, wherein the metal in the catalyst active component precursor is selected from transition metals, preferably selected from copper, silver, gold, zinc, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, lanthanum, cerium, erbium; more preferably selected from copper; and / or 2) The catalyst active component precursor is selected from one or more of the following: metal chlorides, nitrates, sulfates, hydrogen sulfates, phosphates, hydrogen phosphates, dihydrogen phosphates, and complexes of metals with OH and Cl; and / or 3) The mass ratio of the catalyst active component precursor to the carrier is 2.0 to 10.0, or 2.2 to 9.8, or 2.4 to 9.6, or 2.6 to 9.4, or 2.8 to 9.2, or 3.0 to 9.0, or 3.2 to 8.8, or 3.4 to 8.6 and / or 4) The precipitant is selected from metal hydroxides, chlorides, carbonates, bicarbonates, sulfates, bisulfates, phosphates, hydrogen phosphates, or dihydrogen phosphates; Preferably, the precipitant is selected from carbonates, bicarbonates or hydroxides of metals; Preferably, the metal in the precipitant is selected from alkali metals or alkaline earth metals; Preferably, the precipitant is selected from sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, or potassium hydroxide; and / or 5) The mass ratio of the precipitant to the active component precursor is 0.1 to 4, or 0.15 to 3, or 0.2 to 2, or 0.25 to 1.8, or 0.30 to 1.6, or 0.35 to 1.4, or 0.40 to 1.2; and / or 6) The auxiliary agent precursor is selected from oxides, nitrates, phosphates, chlorides, or acetates of transition metals; and / or 7) The transition metal in the auxiliary agent precursor is selected from one or more of zinc, zirconium, molybdenum, titanium, gold, cobalt, lanthanum, or cerium; and / or 8) The mass ratio of the auxiliary agent precursor to the carrier is 0.20 to 4.0, or 0.25 to 3.5, or 0.30 to 3.0, or 0.35 to 2.5; and / or 9) The mass ratio of the precipitant to the auxiliary agent precursor is 0.1 to 10, or 0.2 to 9.5, or 0.3 to 9.0, or 0.4 to 8.5, or 0.5 to 8.0, or 0.6 to 7.5, or 0.7 to 7.0, or 0.8 to 6.5; and / or 10) step i) is carried out at a pH of 7 to 11, or 8 to 10, or 8 to 9; and / or 11) Step i) is carried out under stirring, and the stirring speed is 100 to 500 rpm, or 150 to 400 rpm, or 250 to 350 rpm; and / or 12) step ii) is carried out at a temperature of 200 to 700° C., or 250 to 500° C., or 300 to 400° C.; and / or 13) Step ii) is performed for 1 to 12 hours, or 3 to 8 hours, or 4 to 6 hours.

7. The catalyst as claimed in claim 6, wherein step i) comprises the following sub-steps: i-1) preparing the following third solution and fourth solution, wherein the third solution comprises the catalyst active component precursor and optionally the promoter precursor; the fourth solution comprises the precipitant; i-2) adding the third solution and the fourth solution in parallel to the modified support according to any one of claims 1 to 4; Preferably, step i) has one or more of the following features: 1) In the third solution, the concentration of the active component precursor is 0.2 to 3 mol / L, or 0.5 to 1.5 mol / L, or 1 to 1.5 mol / L; and / or 2) In the third solution, the concentration of the auxiliary agent precursor is 0.2 to 3 mol / L, or 0.5 to 1.5 mol / L, or 1 to 1.5 mol / L; and / or 3) In the fourth solution, the concentration of the precipitant is 0.3 to 3 mol / L, or 0.8 to 2 mol / L, or 1 to 1.8 mol / L; and / or 4) In sub-step ii-2), the flow rate after parallel flow is 1 to 10 mL / min, or 2 to 8 mL / min, or 3 to 7 mL / min.

8. A method for producing a catalyst as claimed in any one of claims 6 to 7, comprising the steps of: i) supporting a catalyst active component precursor and an optional auxiliary agent precursor on the modified carrier according to any one of claims 1 to 4; and ii) subjecting the product of step i) to calcination; Preferably, step i) comprises the following sub-steps: i-1) preparing the following third solution and fourth solution, wherein the third solution comprises the catalyst active component precursor and optionally the promoter precursor; the fourth solution comprises the precipitant; i-2) adding the third solution and the fourth solution in parallel to the modified support according to any one of claims 1 to 4.

9. A method for preparing methanol by hydrogenating CO2, the method using the catalyst as claimed in any one of claims 6 to 7.

10. Use of the catalyst according to any one of claims 6 to 7 or the catalyst produced by the method according to any one of claims 8 in a process for hydrogenating carbon dioxide to methanol.

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