Catalyst for preparing carbonates, method of preparing the catalyst and use thereof

Abstract

Provided is a supported catalyst for preparing carbonates, such as dimethyl carbonate from methyl nitrite and carbon monoxide, including: (a) an active metal component of IUPAC groups 8 to 10; (b) a metal additive selected from at least one of groups 11, 12, 5, 6 and 7; and (c) a modified carrier treated with a non-metallic modifier selected from at least one of groups 15 to 17, wherein, the catalyst has one or more "acidic sites" between 0-500°C as analysed by the NH3-TPD method. The active metal component can be, e.g., rhodium or palladium; the metal additive can be, e.g., copper or zinc; the non-metallic modifier of the modified carrier can be, e.g. ammonia for alumina as carrier or orthophosphoric acid for a silica carrier.

Description

[0001] P139958-TEP

[0002] CATALYST FOR PREPARING CARBONATES AND PREPARATION METHOD AND USE THEREOF

[0003] FIELD

[0004] The present disclosure relates to the technical field of carbonates preparation, and more particularly to a catalyst for preparing carbonates, a method for preparing the catalyst, and a use of the catalyst in preparation of carbonates.

[0005] BACKGROUND

[0006] Carbonates, with a general formula of RO-CO-OR’, are widely utilized as raw materials of engineering plastics, known for their versatility and performance in various applications. The synthesis of carbonates may be achieved through several methods, such as carbonylation method, phosgene method, transesterification method, and carbon dioxide method, among them, the phosgene method is hampered by the high toxicity of its raw materials, while the transesterification and carbon dioxide methods are limited by high raw material costs and low reaction efficiency.

[0007] Therefore, there is still a need for providing a catalyst for preparing carbonates, with higher specificity, better stability, and longer lifespans.

[0008] SUMMARY

[0009] Embodiments of the present disclosure seek to solve at least one of the problems existing in the related art to at least some extent.

[0010] According to a first aspect of the present disclosure, a catalyst for preparing carbonates is provided. The catalyst for preparing carbonates includes: (a) an active metal component of group VIII B; (b) a metal additive selected from at least one of group I B, II B, V B, VI B and VII B; and (c) a modified carrier treated with a non-metallic modifier selected from at least one of group V A, VI A and VII A, wherein, the catalyst has one or more acidic sites between 0-500 °C, and wherein, the active metal component is of 0.1wt%-10wt% by a total solid weight of the catalyst, the metal additive is of 0.1wt%-10wt% by a total solid weight of the catalyst, the non-metallic modifier is of 1wt%-10wt% by a weight of the modified carrier. The catalyst provided in the embodiments of the present disclosure exhibits excellent catalytic activity, selectivity, stability, as well as longer lifespans, for preparing carbonates through the carbonylation reaction of nitrite ester and carbon monoxide.

[0011] In some embodiments, wherein the catalyst has a specific surface area in a range of 10-200 m2 / g, and / or a pore volume in a range of 1-10 cm3 / g, and / or an average pore size is in a range of 1-50 nm. The catalyst provided in the embodiments of the present disclosure with such specific surface area, pore volume, and average pore size may allow for efficient transport of reactants and products through their pores, leading to improved mass transfer.

[0012] In some embodiments, wherein the catalyst has one or two acidic sites between 50-400 °C, optionally as analyzed by NH3-TPD method. The catalyst provided in the embodiments of the present disclosure may effectively anchor active components and additives, and promote the main reaction simultaneously, based on the acidic sites within said range.

[0013] In some embodiments, wherein the active metal component comprises a compound containing Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, or a combination thereof. In some embodiments, for the active metal component, the compound is a salt selected from one or more of nitrate, halide, sulfate, phosphate, and metal complexes. In some embodiments, the compound is nitrate or sulfate. In some embodiments, the compound is nitrate. In some embodiments, for the active metal component, the compound is one or more selected from Rh(NO3)3, PdCl2, PtCl4, and Fe(NO3)3. With the specific active metal component having features above, the catalyst provided in the embodiments of the present disclosure may have a significant improved activity. It may be understood that, the catalytic activity of the catalyst comprising the combination of the active metal component and the metal additive may be significantly and unexpectedly superior to that of the active metal component or metal additive alone, even when the number of compound types is the same. This synergy may be attributed to interactions between the metal components, effects of metal-carrier interfaces, which collectively enhance the catalyst's performance.

[0014] In some embodiments, wherein the metal additive comprises a compound containing Cu, Zn, V, Cr, Mn, Ag, Cd, Nb, Mo, Tc, Au, Hg, Ta, W, Re, or a combination thereof. In some embodiments, for the metal additive, the compound is a salt selected from one or more of nitrate, halide, sulfate, phosphate, and metal complexes. In some embodiments, the compound is nitrate or sulfate. In some embodiments, the compound is nitrate. In some embodiments, for the metal additive, the compound is one or more selected from Cu(NO3)3, ZnCl2, Cr(NO3)3, and NiCl2. With the metal additive having features above, the catalyst provided in the embodiments of the present disclosure may have a significant improved catalytic activity. It may be understood that, the catalytic activity of the catalyst comprising the combination of the active metal component and the metal additive may be significantly and unexpectedly superior to that of the active metal component or metal additive alone, even when the number of compound types is the same. This synergy may be attributed to interactions between the metal components, effects of metal-carrier interfaces, which collectively enhance the catalyst's performance.

[0015] In some embodiments, wherein the non-metallic modifier comprises a compound containing N, P, O, S, F, Cl, Br, I, or a combination thereof. In some embodiments, for the non-metallic modifier, the compound is ammonia, oxygen and / or an acid or base selected from one or more of phosphoric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrogen bromide, and hydroiodic acid. In some embodiments, for the non-metallic modifier, the compound is one or more selected from hydrochloric acid, ammonia, and phosphoric acid. With the non-metallic modifier having features above, the catalyst provided in the embodiments of the present disclosure may have a significant improved catalytic activity. It may be understood that, the catalytic activity of the catalyst comprising the combination of the active metal component, the metal additive and the non-metallic modifier may be significantly and unexpectedly superior to that of the active metal component or metal additive or non-metallic modifier alone, even when the number of compound types is the same. The appropriate non-metallic modifier may optimize the active sites of the catalyst, thus collectively enhancing the catalyst's performance with interactions between the metal components and effects of metal-carrier interfaces.

[0016] In some embodiments, wherein the modified carrier is at least one carrier selected from silicon oxide, aluminum oxide, activated carbon, diamond, spinel, and molecular sieve.

[0017] In some embodiments, wherein, the active metal component is of 0.1wt%-5wt% by a total solid weight of the catalyst, wherein, the metal additive is of 0.1 wt%-5wt% by a total solid weight of the catalyst, and wherein, the non-metallic modifier is of 3wt%-10wt% by a weight of the modified carrier.

[0018] In some embodiments, wherein, the active metal component is of 0.1wt%-3wt% by a total solid weight of the catalyst, wherein, the metal additive is of 0.1 wt%-3wt% by a total solid weight of the catalyst, and wherein, the non-metallic modifier is of 5wt%-10wt% by a weight of the modified carrier. With the specific and optimized percentage of the respective components, the catalyst provided in the embodiments of the present disclosure may have a significant improved catalytic activity, better stability, and longer lifespans.

[0019] According to a second aspect of the present disclosure, a method for preparing the catalyst of any embodiment of the first aspect is provided. The method for preparing the catalyst of any embodiment of the first aspect, includes: performing a treatment on a carrier with a non-metallic modifier to obtain a modified carrier, wherein the non-metallic modifier is of 1wt%-10wt% by a weight of the modified carrier, wherein the non-metallic modifier optionally comprises a compound containing N, P, O, S, F, Cl, Br, I, or a combination thereof; impregnating the modified carrier with a impregnating solution comprising an active metal component and a metal additive so that the active metal component is of 0.1wt%-10wt% by a total solid weight of the catalyst, the metal additive is of 0.1wt%-10wt% by a total solid weight of the catalyst, wherein the impregnating solution is derived by dissolving a salt of the active metal component and a salt of the metal additive separately or simultaneously in acid or base; and drying and roasting the carrier to obtain the catalyst, wherein the roasting is performed at a range of 50-400 °C. With the method of the present disclosure, the catalyst for preparing the carbonates having improved selectivity, better stability, and longer lifespans may be prepared.

[0020] In some embodiments, wherein the treatment is (a) steam etching performed at 500-1000 °C in an atmosphere of the non-metallic modifier, or (b) hydrothermal treatment in solution of the non-metallic modifier at 100-200 °C. With the pretreatment on the carrier with a non-metallic modifier, the catalytic activity and selectivity may be improved significantly.

[0021] According to a third aspect of the present disclosure, a use of the catalyst of any embodiment of the first aspect in preparation of carbonates is provided. The use of the catalyst of any embodiment of the first aspect in preparation of carbonates, includes: using nitrite ester and carbon monoxide as raw materials to produce the carbonates in the presence of the catalyst. The catalyst of any embodiment of the first aspect in the present disclosure may exhibit an excellent catalytic activity, selectivity, stability, as well as longer lifespans, for preparing carbonates through the carbonylation reaction of nitrite ester and carbon monoxide.

[0022] In some embodiments, wherein the nitrite ester and carbon monoxide is used in a molar ratio of 10: 1-1: 10, wherein the concentrations of the nitrite ester and carbon monoxide are at 3% -30% respectively, optionally 5% -20%. In some embodiments, wherein the nitrite ester and carbon monoxide is used in a molar ratio of 2: 1-1:2, wherein the concentrations of the nitrite ester and carbon monoxide are at 5% -20%. Said molar ratio of the nitrite ester and carbon monoxide allows for optimizing reactant interaction and product formation within the catalyst's pores, leading to an improved mass transfer and reaction efficiency at lower cost.

[0023] In some embodiments, wherein the nitrite ester is an alkyl ester containing C1-C4. In some embodiments, the nitrite ester is an alkyl ester containing C1-C2. In some embodiments, the nitrite ester is methyl nitrite. Said nitrite ester, related to the molar ratio of reactants, may be effectively used for the application of the present catalyst in preparation of carbonates.

[0024] In some embodiments, wherein, the preparation is performed in a fixed bed or fluidized bed under a condition at 50-200 °C, and / or 0-lMPa and / or with a reaction space velocity between 100h-1-10000h-1. In some embodiments, the preparation is performed in a fixed bed under a condition at 70-150 °C, and / or 0.3-0.8MPa and / or a reaction space velocity between 500h-1-5000h-1. Said reaction condition facilitates the application of the present catalyst in preparation of carbonates.

[0025] It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory only and shall not be construed to limit the present disclosure.

[0026] BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The accompanying drawings are used for a better understanding of embodiments of the present disclosure and shall not construed to limit the present disclosure, in which:

[0028] FIG. 1 is a schematic diagram showing a peak of an acidic site of a catalyst according to an embodiment of the present disclosure.

[0029] DETAILED DESCRIPTION

[0030] Reference will now be made in detail to embodiments. The implementations set forth in the following description of the embodiments do not represent all implementations consistent with the present disclosure.

[0031] Carbonates, with a general formula of RO-CO-OR’, are widely utilized as raw materials of engineering plastics, known for their versatility and performance in various applications. The variety of carbonates includes dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), propylene carbonate (PC), and diphenyl carbonate (DPC). The carbonates can be polymerized to form polycarbonates, which are widely used as engineering plastics.

[0032] The preparation of carbonates may be achieved through various methods, including the carbonylation method using nitrite ester and carbon monoxide, phosgene method, transesterification method, and carbon dioxide method. The phosgene method is known for its highly toxic raw materials, while the transesterification and carbon dioxide methods suffer from high raw material costs and low reaction efficiency. The carbonylation method stands out due to its low raw material costs and mild reaction conditions, but it also faces challenges such as low catalyst activity and poor stability. Consequently, researchers worldwide have been dedicated to developing highly active and long-life catalysts to maximize the advantages of this process.

[0033] Related art describe catalysts that address some but not all of the key requirements for industrial applications, for example, related catalyst's stability has improved in the shortterm about 500 hours, but the total selectivity for MN (methyl nitrite) is still needs further enhancement. Presently, catalysts have been able to meet one or two of demands for long-term stability, improved total selectivity, and prolonged lifespan, but the challenge of developing a catalyst that excels in all three areas persists and requires further research.

[0034] According to a first aspect of the present disclosure, a catalyst for preparing carbonates is provided. The catalyst for preparing carbonates includes: (a) an active metal component of group VIII B; (b) a metal additive selected from at least one of group I B, II B, V B, VI B and VII B; and (c) a modified carrier treated with a non-metallic modifier selected from at least one of group V A, VI A and VII A, wherein, the catalyst has one or more acidic sites between 0-500 °C, and wherein, the active metal component is of 0.1wt%-10wt% by a total solid weight of the catalyst, the metal additive is of 0.1wt%-10wt% by a total solid weight of the catalyst, the non-metallic modifier is of 1wt%-10wt% by a weight of the modified carrier. The catalyst provided in the embodiments of the present disclosure exhibits excellent catalytic activity, selectivity, stability, as well as longer lifespans, for preparing carbonates through the carbonylation reaction of nitrite ester and carbon monoxide.

[0035] In some embodiments, wherein the catalyst has a specific surface area in a range of 10-200 m2 / g, and / or a pore volume in a range of 1-10 cm3 / g, and / or an average pore size is in a range of 1-50 nm. The catalyst provided in the embodiments of the present disclosure with such specific surface area, pore volume, and average pore size may allow for efficient transport of reactants and products through their pores, leading to improved mass transfer.

[0036] In some embodiments, wherein the catalyst has one or two acidic sites between 50-400 °C, optionally as analyzed by NH3-TPD method. The catalyst provided in the embodiments of the present disclosure may effectively anchor active components and additives, and promote the main reaction simultaneously, based on the acidic sites within said range.

[0037] In some embodiments, wherein the active metal component comprises a compound containing Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, or a combination thereof. In some embodiments, for the active metal component, the compound is a salt selected from one or more of nitrate, halide, sulfate, phosphate, and metal complexes. In some embodiments, the compound is nitrate or sulfate. In some embodiments, the compound is nitrate. In some embodiments, for the active metal component, the compound is one or more selected from Rh(NO3)3, PdCl2, PtCl4, and Fe(NO3)3. With the specific active metal component having features above, the catalyst provided in the embodiments of the present disclosure may have a significant improved activity, especially Rh(NO3)3, PdCl2, and PtCl4.

[0038] In some specific embodiments, when the active metal component, such as Rh(NO3)3 is replaced by another active metal component, such as Fe(NO3)3, the catalyst activity significantly decreases.

[0039] Therefore, it may be believed that with the active metal component possessing features above, the catalyst provided in the embodiments of the present disclosure may have a significant improved activity.

[0040] It may be understood that, the catalytic activity of the catalyst comprising the combination of the active metal component and the metal additive may be significantly and unexpectedly superior to that of the active metal component or metal additive alone, even when the number of compound types is the same. This synergy may be attributed to interactions between the metal components, effects of metal-carrier interfaces, which collectively enhance the catalyst's performance.

[0041] In some embodiments, wherein the metal additive comprises a compound containing Cu, Zn, V, Cr, Mn, Ag, Cd, Nb, Mo, Tc, Au, Hg, Ta, W, Re, or a combination thereof. In some embodiments, for the metal additive, the compound is a salt selected from one or more of nitrate, halide, sulfate, phosphate, and metal complexes. In some embodiments, the compound is nitrate or sulfate. In some embodiments, the compound is nitrate. In some embodiments, for the metal additive, the compound is one or more selected from Cu(NO3)3, ZnCl2, Cr(NO3)3, and NiCl2. With the metal additive having features above, the catalyst provided in the embodiments of the present disclosure may have a significant improved catalytic activity.

[0042] In some specific embodiments, when the metal additive, such as Cu(NO3)3, is subtracted, the catalyst activity significantly decreases. Therefore, it may be believed that with the metal additive having features above, the catalyst provided in the embodiments of the present disclosure may have a significant improved activity.

[0043] It may be understood that, the catalytic activity of the catalyst comprising the combination of the active metal component and the metal additive may be significantly and unexpectedly superior to that of the active metal component or metal additive alone, even when the number of compound types is the same. This synergy may be attributed to interactions between the metal components, effects of metal-carrier interfaces, which collectively enhance the catalyst's performance.

[0044] In some embodiments, wherein the non-metallic modifier comprises a compound containing N, P, O, S, F, Cl, Br, I, or a combination thereof. In some embodiments, for the non-metallic modifier, the compound is ammonia, oxygen and / or an acid or base selected from one or more of phosphoric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrogen bromide, and hydroiodic acid. In some embodiments, for the non-metallic modifier, the compound is one or more selected from hydrochloric acid (HCl), ammonia (NH3), and phosphoric acid(H3PO4). With the non-metallic modifier having features above, the catalyst provided in the embodiments of the present disclosure may have a significant improved catalytic activity. It may be understood that, the catalytic activity of the catalyst comprising the combination of the active metal component, the metal additive and the non-metallic modifier may be significantly and unexpectedly superior to that of the active metal component or metal additive or non-metallic modifier alone, even when the number of compound types is the same. The appropriate non-metallic modifier may optimize the active sites of the catalyst, thus collectively enhancing the catalyst's performance with interactions between the metal components and effects of metal -carrier interfaces.

[0045] In some embodiments, wherein the modified carrier is at least one carrier selected from silicon oxide(SiO2), aluminum oxide(Al2O3), activated carbon, diamond, spinel, and molecular sieve, and wherein the carrier is treated with the non-metallic modifier by steam etching and / or hydrothermal solution approach to obtain the modified carrier.

[0046] In some embodiments, wherein, the active metal component is of 0.1wt%-5wt% by a total solid weight of the catalyst, wherein, the metal additive is of 0.1 wt%-5wt% by a total solid weight of the catalyst, and wherein, the non-metallic modifier is of 3wt%-10wt% by a weight of the modified carrier.

[0047] In some embodiments, wherein, the active metal component is of 0.1wt%-3wt% by a total solid weight of the catalyst, wherein, the metal additive is of 0.1 wt%-3wt% by a total solid weight of the catalyst, and wherein, the non-metallic modifier is of 5wt%-10wt% by a weight of the modified carrier. With the specific and optimized percentage of the respective components, the catalyst provided in the embodiments of the present disclosure may have a significant improved catalytic activity, better stability, and longer lifespans.

[0048] According to a second aspect of the present disclosure, a method for preparing the catalyst of any embodiment of the first aspect is provided. The method for preparing the catalyst of any embodiment of the first aspect, includes: a step of performing a treatment on a carrier with a non-metallic modifier to obtain a modified carrier, wherein the non-metallic modifier is of 1wt%-10wt% by a weight of the modified carrier, wherein the treatment is (a) steam etching performed at 500-1000 °C in an atmosphere of the non-metallic modifier, or (b) hydrothermal treatment in solution of the non-metallic modifier at 100-200°C, wherein the non-metallic modifier optionally comprises a compound containing N, P, O, S, F, Cl, Br, I, or a combination thereof; impregnating the modified carrier with a impregnating solution comprising an active metal component and a metal additive so that the active metal component is of 0.1wt%-10wt% by a total solid weight of the catalyst, the metal additive is of 0.1wt%-10wt% by a total solid weight of the catalyst, wherein the impregnating solution is derived by dissolving a salt of the active metal component and a salt of the metal additive separately or simultaneously in acid or base; and drying and roasting the carrier to obtain the catalyst, wherein the roasting is performed at a range of 50-400 °C. With the method of the present disclosure, the catalyst for preparing the carbonates having improved selectivity, better stability, and longer lifespans may be prepared. It may be understood that the specific methods and conditions, such as roasting time, may be adjusted according to actual needs for the treatment provided in embodiments of the present disclosure are only exemplary and not intended to be any limitation, as long as the method allows for the active metal component is of 0.1wt%-10wt% by a total solid weight of the catalyst, the metal additive is of 0.1wt%-10wt% and the non-metallic modifier is of 1wt%-10wt% by a weight of the modified carrier. According to a third aspect of the present disclosure, a use of the catalyst of any embodiment of the first aspect in preparation of carbonates is provided. The use of the catalyst of any embodiment of the first aspect in preparation of carbonates, includes: using nitrite ester and carbon monoxide as raw materials to produce the carbonates in the presence of the catalyst. The catalyst of any embodiment of the first aspect in the present disclosure may exhibit an excellent catalytic activity, selectivity, stability, as well as longer lifespans, for preparing carbonates through the carbonylation reaction of nitrite ester and carbon monoxide.

[0049] In some embodiments, wherein the nitrite ester and carbon monoxide is used in a molar ratio of 10: 1-1: 10, wherein the concentrations of the nitrite ester and carbon monoxide are at 3% -30% respectively, optionally 5% -20%. In some embodiments, wherein the nitrite ester and carbon monoxide is used in a molar ratio of 2: 1-1:2, wherein the concentrations of the nitrite ester and carbon monoxide are at 5% -20%. Said molar ratio of the nitrite ester and carbon monoxide allows for optimizing reactant interaction and product formation within the catalyst's pores, leading to improved mass transfer and reaction efficiency at lower cost.

[0050] In some embodiments, wherein the nitrite ester is an alkyl ester containing C1-C4. In some embodiments, the nitrite ester is an alkyl ester containing C1-C2. In some embodiments, the nitrite ester is methyl nitrite. An nitrite ester being alkyl ester containing C1-C4 refers to an ester with an alkyl group that may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, or 4 carbon atoms; the nitrite ester is an alkyl ester containing C1-C2 refers to an ester with an alkyl group that may have 1 carbon atom, or 2 carbon atom. Said nitrite ester, related to the molar ratio of reactants, may be effectively used for the application of the present catalyst in preparation of carbonates.

[0051] In some embodiments, wherein, the preparation is performed in a fixed bed or fluidized bed under a condition at 50-200 °C, 0-lMPa and with a reaction space velocity between lOOh' OOOOh" f In some embodiments, the preparation is performed in a fixed bed under a condition at 70-150 °C, 0.3-0.8MPa and a reaction space velocity between 500h-1-5000h-1. Said reaction condition facilitates the application of the present catalyst in preparation of carbonates.

[0052] Example

[0053] The following Examples are included to demonstrate certain aspects and embodiments of the present disclosure. It should be appreciated by those of skill in the art, however, that the following description is illustrative only and should not be taken in any way as a restriction of the present disclosure.

[0054] Test methods

[0055] The substances used in the following examples all meet chemically pure standards, and are conventional products that may be obtained through commercial product. The reaction conditions are conventional condition commonly known unless specified additionally, such as, atmospheric pressure, and the like.

[0056] The metal and non-metal content of the catalyst were quantitatively analyzed with an Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES, Agilent Technologies, Inc.), Bruker tabletop X-ray fluorescence analyzer (Bruker Corporation), and EuroEA3000 elemental analyzer (Euro Vector), and specific operations are referred to the manufacturer's manual correspondingly.

[0057] The acidic sites of the catalyst were analyzed using a Micromeritics Chemisorption Analyzer 2920 (Micromeritics Instrument Corporation), with the specific procedure set as follows: the heating rate was 2 °C / min, and the temperature was ranged in 0-1000 °C

[0058] The specific surface area, pore volume, and pore size of the catalyst were determined using a Micromeritics Physical Adsorption Analyzer ASAP2460 (Micromeritics Instrument Corporation).

[0059] The compositions of the reaction solution were analyzed using a gas chromatograph GC-2014 (Shimadzu Corporation). The space-time yield (STY) of the catalyst was calculated using Formula (1) to compare catalytic activity, and the selectivity of products was calculated using Formula (2) as follows:

[0060] TV 4 ■; > mass of main product (g)

[0061] i l g*L *n ) —cata|ystvolume (L)xtime (h) > Formula (1);

[0062] Selectivity I motes of rear / tants

[0063] ‘

[0064]

[0065] I teiai moies of reactant involved /

[0066] > Formula (2). Example 1

[0067] i) Preparation of Catalyst A

[0068] The Catalyst A was prepared according to reaction system and treatment procedure according to Table 1-1 as follows. Table 1-1

[0069] Step Substance Mass (g) Treatment Modifying., _. _ Ammonia treatment at

[0070]

[0071] treatment 800 °C for 3 hours

[0072] Rh (NO3)31

[0073] T. CU(NO3)2 1 Stirring at 50 °C for 10 hours Impregnating ' '

[0074] treatment 10wt%HCl 20

[0075] Impregnating at 50 C for 1 Modified carrier 30,

[0076] hour

[0077] Drying and _.,

[0078] . „. Drying, and then roasting at roasting Catalyst A 200 »C for 2 hours

[0079] treatment

[0080] ii) Analysis of Catalyst A

[0081] Catalyst A was analyzed according to the test methods described above, and the mass percentage of the respective components were listed as table 1-2 and the properties of the Catalyst A were listed as table 1-3.

[0082] Table 1-2

[0083] Element Mass(g) Percentage(%)

[0084] Rh 0.36 1.05

[0085] Cu 0.34 1.00

[0086] N 2.39 7.04

[0087] Cl 1.95 5.72

[0088] N-non-metallic modifier 3.50 7.00

[0089] Total up 34.00

[0090] Table 1- 3

[0091] Specif11:,z_ AverageAcidic site- Acidic sitesurface area Pore volume (cm / g) pore sizekl ( ) peak2 CC)

[0092]

[0093] (m7g) (nm)

[0094] 150 7 20 223 311

[0095] Additionally, FIG. 1 was a schematic diagram showing a peak of an acidic site of the catalyst A.

[0096] iii) Catalyst evaluation of Catalyst A

[0097] The performance of Catalyst A was evaluated under the catalyst evaluation conditions as Table 1-4, and the performance results of Catalyst A were shown as table 1-5. It should be understood that, dimethyl carbonate was obtained using MN and CO as raw materials. Therefore, both spatial-time yield and selectivity were calculated based on the obtained target product dimethyl carbonate.

[0098] Table 1-4

[0099] Catalyst Evaluation Conditions

[0100] MN Concentration (%) 12

[0101] CO Concentration (%) 12

[0102] Temperature (°C) 130

[0103] Pressure (MPa) 05

[0104] Velocityfh’1) 4000

[0105] Table 1-5

[0106] STY g-L- Time

[0107]

[0108] ^h1Selectivity %

[0109] 5h 950 99

[0110] 2000h 941 98.8

[0111] Example 2

[0112] i) Preparation of Catalyst B

[0113] The Catalyst B was prepared according to reaction system and treatment procedure according to Table 2-1 as follows.

[0114] Table 2-1

[0115] Step Substance Mass (g) Treatment

[0116] 30 wt% Phosphoric acid Modifying treatment SiO2 50 treatment at 150°C for 10

[0117] hours

[0118] PdCl20.1

[0119] ZnCl20.1 Stirring at 80 °C for 5 hours

[0120]

[0121] Impregnating treatment, 20

[0122] HC1

[0123] Modified Impregnating at 80 °C for 3

[0124]

[0125] carrier hours

[0126] Drying and roasting. Drying, and then roasting at treatment

[0127]

[0128] a a ys 300 °C for 1 hour

[0129] ii) Analysis of Catalyst B

[0130] Catalyst B was analyzed according to the test methods described above, and the mass percentage of the respective components were listed as table 2-2, and the properties of the Catalyst B were listed as table 2-3.

[0131] Table 2-2

[0132] Element Mass(g) Percentage(%)

[0133] Pd 0.06 0.19

[0134] Zn 0.05 0.15

[0135] P-non- metallic 3.00 6.00

[0136] modifier

[0137] Cl 2.04 6.33

[0138] Total up 32.2

[0139] Table 2-3

[0140] Pore Average...

[0141] Specific surface.. Acidic site- Acidic site- area (m2 / g) peak 1 (°C) peak2 (°C)

[0142]

[0143] 100 5 15 190 300 iii) Catalyst evaluation of Catalyst B

[0144] The performance of Catalyst B was evaluated under the catalyst evaluation conditions as Table 2-4, and the performance results of Catalyst B were shown as table 2-5.

[0145] Catalyst Evaluation Conditions

[0146] MN Concentration (%) 12

[0147] CO Concentration (%) g

[0148] Temperature (°C) 150

[0149] Pressure (MPa) 03

[0150] Velocity(h-1) 2000

[0151] Table 2-5

[0152] STY g-L- Time

[0153]

[0154] ^h1Selectivity %

[0155] 5h 630 97.5

[0156] 2000h 610 97

[0157] Example 3

[0158] i) Preparation of Catalyst C

[0159] The Catalyst C was prepared according to reaction system and treatment procedure according to Table 3-1 as follows. Table 3-1

[0160] Step Substance Mass (g) Treatment

[0161] ,t. Ammonia treatment Modifyinglnel at 500 for 5treatment

[0162]

[0163] hours

[0164] PtCl41.8

[0165] Cr(NO3)31 Stirring at 30 °C for

[0166] . 15wt% I5hours

[0167] ImpregnatingHCJ 20

[0168] LieaLmenL

[0169] Modified Impregnating at

[0170]

[0171] carrier 30 °C for 5 hours

[0172] , Drying, and then

[0173] ■. Catalyst C roasting at 100 C roasting treatment „,,

[0174] tor 1 hour

[0175] ii) Analysis of Catalyst C

[0176] Catalyst C was analyzed according to the test methods described above, and the mass percentage of the respective components were listed as table 3-2 and the properties of the Catalyst C were listed as table 3-3.

[0177] Table 3-2

[0178] Element Mass(g) Percentage(%)

[0179] Pt 1.04 2.91

[0180] Cr 0.22 0.61

[0181] N 1.68 4.68

[0182] Cl 3.68 10.27

[0183] N-non-metallic 59 5 99

[0184] modifier

[0185] Total up 35.80

[0186] Table 3- 3

[0187] Specific surface..,,,.. Average Acidic site- Acidic sitearea (n / g) Pore volume (cm / g) pore zepeakl (»c) peak2 (»c)

[0188]

[0189] 120 5 18 200 315

[0190] iii) Catalyst evaluation of Catalyst C

[0191] The performance of Catalyst C was evaluated under the catalyst evaluation conditions as Table 3-4, and the performance results of Catalyst C were shown as table 3-5. Table 3-4

[0192] Catalyst Evaluation Conditions

[0193] MN Concentration (%) 6

[0194] CO Concentration (%) 12

[0195] Temperature (°C) 70

[0196] Pressure (MPa) 0.8

[0197] Velocity(h-1) 5000

[0198] Table 3-5

[0199] STY g-L- Time

[0200]

[0201] ^h1Selectivity %

[0202] 5h 781 97.3

[0203] 2000h 775 97

[0204] Example 4

[0205] i) Preparation of Catalyst D

[0206] The Catalyst D was prepared according to reaction system and treatment procedure according to Table 4-1 as follows.

[0207] Table 4-1

[0208] Step Substance Mass (g) Treatment Ammonia

[0209] ,,.,, • treatment at Modifying treatment molecular sieve 50

[0210]

[0211] OQ fQr

[0212] 1 hour

[0213] PtCl40.5

[0214] Cu z(NxiO3i)233St()irr0i(n,gfoatr

[0215] N1C12 0 515 hours Impregnating treatment 10wt% HCl 20

[0216] Impregnating Modified carrier 30 at 30 °C for

[0217] 5 hours

[0218] Drying, and Drying and roasting „, _ then roasting treatment Catalyst D at 100 °C

[0219] for 1 hour

[0220] ii) Analysis of Catalyst D

[0221] Catalyst D was analyzed according to the test methods described above, and the mass percentage of the respective components were listed as table 4-2 and the properties of the Catalyst D were listed as table 4-3.

[0222] Table 4-2

[0223] Element Mass(g) Percentage(%)

[0224] Pt 0.29 0.80

[0225] Cu 1.02 2.82

[0226] Ni 0.23 0.63

[0227] N 3.33 9.24

[0228] Cl 2.43 6.75

[0229] N-non- metallic 4.80 9.60

[0230] modifier

[0231] Total up 36.00

[0232] Table 4- 3

[0233] Specific surfaceP.OreAverage

[0234]

[0235] Ac;s,te_ Acidic sitearea (n / g) Pore sizepeakl CC ) peak2 (°C)v 07(cm / g)

[0236]

[0237] (nm) 165 8 21 240 338

[0238] iii) Catalyst evaluation of Catalyst D

[0239] The performance of Catalyst D was evaluated under the catalyst evaluation conditions as Table 4-4, and the performance results of Catalyst D were shown as table 4-5.

[0240] Table 4-4

[0241] Catalyst Evaluation Conditions

[0242] MN Concentration (%) 12

[0243] CO Concentration (%) 12

[0244] Temperature (°C) 130

[0245] Pressure (MPa) 0.5

[0246] Velocity(h-l) 4000

[0247] Table 4-5

[0248] STY g-L-

[0249]

[0250] Time ^h1Selectivity %

[0251] 5h 675 97.8

[0252] 2000h 662 97.5

[0253] Comparative Example 1 i) Preparation of Catalyst E

[0254] The Catalyst E was prepared according to reaction system and treatment procedure according to Table 5-1 as follows.

[0255] Table 5-1

[0256] Step Substance Mass (g) Treatment Modifying treatment SiCh 50 None

[0257] Rh(NO3)3 1 Stirring at

[0258] 10wt%9050 °C for

[0259] HC1 10 hours

[0260] Impregnating treatment

[0261] Impregnating

[0262] Modified 30 at 50 C r for

[0263] earner

[0264] 1 hour

[0265] Drying, and

[0266] Drying and roasting „. then roasting treatment Catalyst Eat 200°C

[0267] for 2 hour

[0268] ii) Analysis of Catalyst E

[0269] Catalyst E was analyzed according to the test methods described above, and the mass percentage of the respective components were listed as table 5-2 and the properties of the Catalyst E were listed as table 5-3.

[0270] Table 5-2

[0271] Element Mass(g) Percentage(%)

[0272] Rh 0.36 1.08

[0273] N 0.15 0.44

[0274] Cl 1.95 5.89

[0275] Total up 33.00

[0276] Table 5- 3

[0277] Specific surface areaP.oreAverage Acidic site- (m2 / g) vo'umeP°repeak 1 (°C)

[0278] (cm / g) (nm)

[0279] 80 4 10 300

[0280] iii) Catalyst evaluation of Catalyst E

[0281] The performance of Catalyst E was evaluated under the catalyst evaluation conditions as Table 5-4, and the performance results of Catalyst E were shown as table 5-5. Table 5-4

[0282] Catalyst Evaluation Conditions

[0283] MN Concentration (%) 12

[0284] CO Concentration (%) 12

[0285] Temperature (°C) 130

[0286] Pressure (MPa) 0.5

[0287] Velocity(h-1) 4000

[0288] Table 5-5

[0289] STY g-L- Time

[0290]

[0291] ^h1Selectivity %

[0292] 5h 584 85.1

[0293] 2000h 301 56.7

[0294] Comparative Example 2

[0295] i) Preparation of Catalyst F

[0296] The Catalyst F was prepared according to reaction system and treatment procedure according to Table 6-1 as follows.

[0297] Table 6-1

[0298] Step Substance Mass (g) Treatment Modifying treatment SiO2 50 None

[0299] FefNCh 1 Stirring at

[0300] Cu(NO3)21 50 °C for

[0301] H2O 20 10 hours

[0302] impregnating ircai cni

[0303] Impregnating

[0304] Modified 30 at 50 C r for

[0305] carrier

[0306] 1 hour

[0307] Drying, and

[0308] Drying and roasting „, „ then roasting treatment Catalyst fat 200oC

[0309] for 2 hour

[0310] ii) Analysis of Catalyst F

[0311] Catalyst F was analyzed according to the test methods described above, and the mass percentage of the respective components were listed as table 6-2 and the properties of the Catalyst F were listed as table 6-3. Table 6-2

[0312] Element Mass(g) Percentage(%)

[0313] Fe 0.23 0.72

[0314] Cu 0.34 1.06

[0315] N 0.32 1.01

[0316] Total up 32.00

[0317] Table 6- 3

[0318] Specific surface areaPoiAverage Acidic site- im’ / g, T6peak 1 (°C)

[0319] (cm 7g) (nm)

[0320] 75 9 10 NONE

[0321] iii) Catalyst evaluation of Catalyst F

[0322] The performance of Catalyst F was evaluated under the catalyst evaluation conditions as Table 6-4, and the performance results of Catalyst F were shown as table 6-5.

[0323] Table 6-4

[0324] Catalyst Evaluation Conditions

[0325] MN Concentration (%) 12

[0326] CO Concentration (%) 12

[0327] Temperature (°C) 130

[0328] Pressure (MPa) 05

[0329] Velocity(h-l) 4000

[0330] Table 6-5

[0331] STY g-L- Time

[0332]

[0333] ^h1Selectivity %

[0334] 5h 613 90.2

[0335] 2000h 256 51.2

[0336] According to the evaluation results of the catalysts provided in the example 1-4 based on the present disclosure and the comparative examples, the performances of catalysts A-F were compared. The catalysts A-D included the active metal component, the metal additive and the modified carrier treated with a non-metallic modifier simultaneously. The catalyst E included the active metal component and the modified carrier not treated with a non-metallic modifier. The catalyst F included the active metal component, the metal additive and the modified carrier but not treated with a non-metallic modifier.

[0337] As results, during 5 hours and 2000 hours, the catalysts A-D show no significant differences in catalytic performances, indicating the long-term stability and better lifespan of the catalysts. As results, the catalysts A-D show higher STY and Selectivity for MN than that of catalysts E-F, indicating key role of the components of the active metal component, the metal additive and the non-metallic modifier

[0338] By comparing the catalysts prepared in the above examples and comparative examples, it can be concluded that the catalyst prepared by the present disclosure has an excellent catalytic activity, stability, and selectivity.

[0339] Terms used herein in embodiments of the present disclosure are only for the purpose of describing specific embodiments, but should not be construed to limit the present disclosure. As used in the embodiments of the present disclosure and the appended claims, “a / an”, and “the” in singular forms are intended to include plural forms, unless clearly indicated in the context otherwise. It should also be understood that, the term “and / or” used herein represents and contains any or all possible combinations of one or more associated listed items.

[0340] When term “about” is used, this term may mean that there can be a variance in value of up to ±10%, of up to 5%, of up to 2%, of up to 1%, of up to 0.5%, of up to 0.1%, or up to 0.01%. Term “range” disclosed in the present disclosure is defined in the form of a lower limit and an upper limit, 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 special range. The range defined in this way can be inclusive or exclusive, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is understood that ranges of 60-110 and 80-120 are also obtained. In addition, if the listed minimum values are 1 and 2, and if the listed maximum values are 3, 4 and 5, the ranges of 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5 may be obtained. In the present disclosure, unless otherwise specified, the numerical range “a-b” means the abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range “0-5” means that all the real numbers between “0-5” have been listed, and “0-5” is only the abbreviated representation of these numerical combinations. In addition, when a parameter is 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.

[0341] Reference throughout this specification to “an embodiment,” “some embodiments,” “one embodiment”, “another example,” “an example,” “a specific example,” or “some examples,” means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. Thus, the appearances of the phrases such as “in some embodiments,” “in one embodiment”, “in an embodiment”, “in another example,” “in an example,” “in a specific example,” or “in some examples,” in various places throughout this specification are not necessarily referring to the same embodiment or example of the present disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments or examples.

[0342] Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed here. This application is intended to cover any variations, uses, or adaptations of the disclosure following the general principles thereof and including such departures from the present disclosure as come within known or customary practice in the art. It is intended that the specification and examples be considered as illustrative only, with a true scope and spirit of the disclosure being indicated by the following claims.

Claims

CLAIMS1. A catalyst for preparing carbonates, comprising:(a) an active metal component of group VIII B;(b) a metal additive selected from at least one of group I B, II B, V B, VI B and VII B; and (c) a modified carrier treated with a non-metallic modifier selected from at least one of group V A, VI A and VII A,wherein, the catalyst has one or more acidic sites between 0-500 °C, andwherein, the active metal component is of 0.1wt%-10wt% by a total solid weight of the catalyst, the metal additive is of 0.1wt%-10wt% by a total solid weight of the catalyst, the non-metallic modifier is of 1wt%-10wt% by a weight of the modified carrier.

2. The catalyst of claim 1, wherein the catalyst has a specific surface area in a range of 10-200 m2 / g, and / or a pore volume in a range of 1-10 cm3 / g, and / or an average pore size is in a range of 1-50 nm.

3. The catalyst of claim 1 or 2, wherein the catalyst has one or two acidic sites between 50-400 °C, optionally as analyzed by NH3-TPD method.

4. The catalyst of any one of claims 1 to 3, wherein the active metal component comprises a compound containing Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, or a combination thereof, and optionally, for the active metal component, the compound is a salt selected from one or more of nitrate, halide, sulfate, phosphate, and metal complexes, more optionally the compound is nitrate or sulfate, more optionally the compound is nitrate,optionally, for the active metal component, the compound is one or more selected from Rh (NO3)3, PdCl2, PtCl4, and Fe(NO3)3.

5. The catalyst of any one of claims 1 to 4, wherein the metal additive comprises a compound containing Cu, Zn, V, Cr, Mn, Ag, Cd, Nb, Mo, Tc, Au, Hg, Ta, W, Re, or a combination thereof, andoptionally, for the metal additive, the compound is a salt selected from one or more of nitrate,halide, sulfate, phosphate, and metal complexes, more optionally the compound is nitrate or sulfate, more optionally the compound is nitrate,optionally, for the metal additive, the compound is one or more selected from Cu(NO3)3, ZnCl2, Cr(NO3)3, and NiCl2.

6. The catalyst of any one of claims 1 to 5, wherein the non-metallic modifier comprises a compound containing N, P, O, S, F, Cl, Br, I, or a combination thereof,optionally, for the non-metallic modifier, the compound is ammonia, oxygen and / or an acid or base selected from one or more of phosphoric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrogen bromide, and hydroiodic acid,optionally, for the non-metallic modifier, the compound is one or more selected from hydrochloric acid, ammonia, and phosphoric acid.

7. The catalyst of any one of claims 1 to 6, wherein the modified carrier is at least one carrier selected from silicon oxide, aluminum oxide, activated carbon, diamond, spinel, and molecular sieve.

8. The catalyst of any one of claims 1 to 7,wherein, the active metal component is of 0.1 wt%-5wt% by a total solid weight of the catalyst, wherein, the metal additive is of 0.1 wt%-5wt% by a total solid weight of the catalyst, and wherein, the non-metallic modifier is of 3wt%-10wt% by a weight of the modified carrier, and optionally,wherein, the active metal component is of 0.1 wt%-3wt% by a total solid weight of the catalyst, wherein, the metal additive is of 0.1 wt%-3wt% by a total solid weight of the catalyst, and wherein, the non-metallic modifier is of 5wt%-10wt% by a weight of the modified carrier.

9. A method for preparing the catalyst of any one of claim 1 to 8, comprising: performing a treatment on a carrier with a non-metallic modifier to obtain a modified carrier, wherein the non-metallic modifier is of lwt%-10wt% by a weight of the modified carrier, wherein the non-metallic modifier optionally comprises a compound containing N, P, O, S, F, Cl, Br, I, or a combination thereof;impregnating the modified carrier with a impregnating solution comprising an active metal component and a metal additive, so that the active metal component is of 0.1wt%-10wt% by a total solid weight of the catalyst, the metal additive is of 0.1wt%-10wt% by a total solid weight of the catalyst, wherein the impregnating solution is derived by dissolving a salt of the active metal component and a salt of the metal additive separately or simultaneously in acid or base; and drying and roasting the carrier to obtain the catalyst, wherein the roasting is performed at a range of 50-400 °C.

10. The method of claim 9, wherein the treatment is (a) steam etching performed at 500-1000 °C in an atmosphere of the non-metallic modifier, or (b) hydrothermal treatment in solution of the non-metallic modifier at 100-200 °C.

11. Use of the catalyst of any one of claims 1 to 8 in preparation of carbonates, comprising: using nitrite ester and carbon monoxide as raw materials to produce the carbonates in the presence of the catalyst.

12. The use of claim 11, wherein the nitrite ester and carbon monoxide is used in a molar ratio of 10:1-1:10, optionally 2: 1-1:2, wherein the concentrations of the nitrite ester and carbon monoxide are at 3% -30% respectively, optionally 5% -20%,13. The use of claim 11 or 12, wherein the nitrite ester is an alkyl ester containing C1-C4, optionally the nitrite ester is an alkyl ester containing C1-C2, more optionally, the nitrite ester is methyl nitrite.

14. The use of any one of claims 11 to 13, wherein, the preparation is performed in a fixed bed or fluidized bed under a condition at 50-200 °C, and / or 0-lMPa and / or with a reaction space velocity between 100h-1-10000h-1,optionally the preparation is performed in a fixed bed under a condition at 70-150 °C, and / or 0.3-0.8MPa and / or a reaction space velocity between 500h-1-5000h-1.

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