A sulfur-tolerant hydrodechlorination catalyst with core-shell structure, and a preparation method and application thereof

Abstract

The application provides a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure and a preparation method and application thereof. The sulfur-tolerant hydrogenation dechlorination catalyst is prepared by an impregnation method, a carrier is C12A7 with a cage structure as a core, and TiO2 is a shell layer; the cage structure of C12A7 has abundant micro-channels, facilitates the entry of Cl ‑ , O 2‑ , and simultaneously provides a larger reaction surface; the TiO2 shell layer is together with an active component to form a hydrogenation dechlorination active center; the three components have a synergistic effect, that is, the hydrogenation dechlorination activity is improved, and the activity stability in a chlorine-containing atmosphere is maintained; the sulfur-tolerant hydrogenation dechlorination catalyst can tolerate sulfur: suitable for a sulfur-containing atmosphere, and has no upper limit for sulfur tolerance; the sulfur-tolerant hydrogenation dechlorination catalyst has good activity stability: resistant to HCl and other gases that are toxic to the catalyst; and the sulfur-tolerant hydrogenation dechlorination catalyst with the core-shell structure has high strength, and the particle crushing strength is greater than or equal to 100 N / cm.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of hydrogenation dechlorination catalysts, in particular to a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure and a preparation method and application thereof. BACKGROUND

[0002] In recent years, as high-quality low-chlorine coal resources are gradually depleted, high-chlorine coal is used partially or entirely to replace low-chlorine coal as a gas-making raw material. As a typical low-quality coal, chlorine in the coal can be released in the form of HCl, Cl2 and organic chlorine in the gasification process, and is taken to the downstream with the raw material gas, causing rapid deactivation of the catalyst in the downstream.

[0003] The inorganic chlorine (HCl, Cl2) can be effectively removed by water washing, dry dechlorination and the like, while the organic chlorine has no effective removal method at present.

[0004] If a hydrogenation dechlorination catalyst can be developed to convert the organic chlorine in the coal gas into inorganic chlorine (HCl), which is then effectively removed by water washing, dry dechlorination and the like, the chlorine poisoning and deactivation of the catalyst in the downstream and the corrosion of the equipment caused by chlorine can be avoided, and the safety operation period of the enterprise is obviously improved, and the economic and social benefits are improved.

[0005] At present, there are few reports on hydrogenation dechlorination catalysts for organic chlorine in coal gas at home and abroad. The prior art discloses a 1,2-dichloroethane selective hydrogenation dechlorination catalyst, which uses titanium dioxide as a carrier and a noble metal (Pd, Pt, Au or Ru) as an active component, is expensive and not sulfur-tolerant. The prior art discloses a catalyst for catalytic hydrogenation dechlorination, which uses activated carbon, silicon carbide or a mixture of the two as a carrier and a noble metal Ru as an active component, and also has the problems of high price and poor sulfur tolerance. The prior art discloses a method for catalytic hydrogenation dechlorination, which uses a nickel carbide nanocomposite as a catalyst, has a complex preparation process, is high in price and only suitable for liquid-phase hydrogenation dechlorination, and is not sulfur-tolerant. The prior art discloses a catalytic hydrogenation dechlorination catalyst, which uses alumina as a carrier and is suitable for hydrogenation dechlorination of waste plastic cracking oil, and has a high reaction temperature (320℃). The prior art discloses a coking crude benzene hydrogenation dechlorination catalyst, which uses Al2O3-SiO2 as a carrier and a mixture of nickel oxide, palladium oxide and molybdenum trioxide as an active component, is high in price and not sulfur-tolerant. The prior art discloses a carbon-supported hydrogenation dechlorination catalyst, which uses activated carbon as a carrier and a noble metal Ru as an active component, has a complex preparation process, is high in price and not sulfur-tolerant.

[0006] Therefore, the current research on the sulfur-tolerant hydrogenation dechlorination catalysts applied to the sulfur-containing coal gas atmosphere is still insufficient, most of the reported hydrogenation dechlorination catalysts use noble metals as the active components, which are expensive, not sulfur-tolerant and cannot be widely applied, and therefore it is of great practical significance to develop a sulfur-tolerant hydrogenation dechlorination catalyst with high activity, moderate price and suitable for the removal of organic chlorine in the sulfur-containing coal gas. SUMMARY

[0007] The sulfur-tolerant hydrogenation dechlorination catalyst and the preparation method thereof are provided, the hydrogenation dechlorination catalyst is a supported catalyst, the carrier has a core of 12CaO·7Al2O3 (C12A7) with a cage structure and a shell of TiO2, and the active elements in the active component include Co and / or Ni and Mo and / or W.

[0008] To achieve the above object, the present application adopts the following technical scheme:

[0009] In the first aspect, the present application provides a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure, which comprises a carrier and an active component supported on the carrier.

[0010] The carrier comprises a core layer and a shell layer coated on the core layer.

[0011] The core layer is 12CaO·7Al2O3 (C12A7) with a cage structure.

[0012] The shell layer is TiO2.

[0013] The active elements in the active component include Co and / or Ni and Mo and / or W.

[0014] Preferably, the mass fraction of the shell layer in the carrier is 10-25%.

[0015] The sum of the mass of the Co element and the Ni element is 2-4% of the mass of the carrier, and the mass ratio of the Co element to the Ni element is (0-1.6):(0-1.6); the sum of the mass of the Mo element and the W element is 4-15% of the mass of the carrier, and the mass ratio of the Mo element to the W element is (0-5):(0-5).

[0016] In the second aspect, the present application further provides a preparation method of the sulfur-tolerant hydrogenation dechlorination catalyst with the core-shell structure, which comprises the following steps:

[0017] After mixing the Co source and / or the Ni source with the Mo source and / or the W source, ammonia water is added, and stirring is performed to obtain an impregnation solution;

[0018] The carrier is added to the impregnation solution, stirring is performed, and then drying is performed to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure.

[0019] Preferably, the carrier is added to the impregnation solution, stirring is performed, and then drying is performed at 100-150 ℃ for 2-12 h to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure.

[0020] Preferably, the Co source is cobalt nitrate;

[0021] The Ni source is nickel nitrate;

[0022] The Mo source is ammonium heptamolybdate;

[0023] The W source is ammonium tungstate.

[0024] Preferably, cobalt nitrate, nickel nitrate, ammonium heptamolybdate, and ammonium tungstate are mixed, ammonia water is added, and stirring is performed to obtain an impregnation solution; the carrier is added to the impregnation solution, and stirring is performed to obtain an impregnated carrier.

[0025] The mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, the ammonium tungstate, the carrier, and the ammonia water is (0-5) g:(0-5) g:(0-65) g:(0-61) g:(50-60) g:(20-25) mL;

[0026] The ratio of the sum of the mass of the cobalt nitrate and the nickel nitrate to the mass of the carrier is (3.5-6.5):(50-60);

[0027] The ratio of the sum of the mass of the ammonium heptamolybdate and the ammonium tungstate to the mass of the carrier is (30-65):(50-60);

[0028] The mass concentration of the ammonia water is 20-30%.

[0029] Preferably, the preparation method of the carrier comprises the following steps:

[0030] Preparation of dodecacalcium heptanium with a cage cavity structure;

[0031] After mixing dodecacalcium heptanium with a cage cavity structure and a titanium source, water is added, and kneading is performed to obtain a mixture;

[0032] The mixture is dried and then calcined to obtain a carrier.

[0033] Preferably, the titanium source is titanium sol;

[0034] The mass ratio of the titanium dioxide, water and the seven calcium dodecaaluminate with cage cavity structure in the step of kneading the seven calcium dodecaaluminate with cage cavity structure and the titanium source after mixing and adding water is (75-90):(10-25):(40-60);

[0035] The drying temperature in the step of drying the mixture is 100-150 DEG C, and the drying time is 2-12h;

[0036] The calcination temperature in the step of calcining the mixture after drying is 400-500 DEG C, and the calcination time is 2-4h;

[0037] The preparation method of the seven calcium dodecaaluminate with cage cavity structure comprises the following steps:

[0038] Mixing the aluminum source and the calcium source to obtain a mixed powder;

[0039] Adding nitric acid into water to obtain an acid solution;

[0040] Adding the mixed powder into the acid solution and mixing to obtain a wet powder;

[0041] Drying the wet powder at 100-150 DEG C for 2-12h, and then calcining at 600-700 DEG C for 2-4h to obtain the seven calcium dodecaaluminate with cage cavity structure;

[0042] The aluminum source comprises aluminum hydroxide and / or pseudo-boehmite;

[0043] The calcium source comprises at least one of calcium carbonate, calcium hydroxide and calcium oxide;

[0044] The molar ratio of aluminum in the aluminum source to calcium in the calcium source is 7:6;

[0045] In the step of adding nitric acid into water, the nitric acid is a nitric acid solution with a mass fraction of 65-68%, and the mass ratio of the nitric acid solution to water is (3-5):(48-50);

[0046] In the steps of mixing the aluminum source and the calcium source to obtain a mixed powder and adding nitric acid into water, the molar ratio of aluminum in the aluminum source to water is 1:(2.67-2.78).

[0047] In a third aspect, the application further provides an application of the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure or the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure prepared by the preparation method in removing organic chlorine in sulfur-containing coal gas.

[0048] Preferably, in the application, the use conditions of the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure are as follows: the use atmosphere is sulfur-containing coal gas, the reaction temperature is 180-320 DEG C, the space velocity is 500-3000h -1 .

[0049] The sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure and the preparation method thereof have the following beneficial effects relative to the prior art:

[0050] The sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure is prepared by the impregnation method, the carrier takes C12A7 with cage structure as the core and takes TiO2 as the shell layer, and the catalyst has the core-shell structure; the C12A7 with cage structure has abundant micro-channels, which facilitates the entry of Cl - , O 2- , and provides more reaction surface; the TiO2 as the shell layer, together with the active components, forms the hydrogenation dechlorination active center; the three components have a synergistic effect, that is, the hydrogenation dechlorination activity is improved, and the activity stability in the chlorine-containing atmosphere is maintained; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure has high activity, due to the unique core-shell structure, the three components have a synergistic effect, that is, the hydrogenation dechlorination activity is improved, and the activity stability in the chlorine-containing atmosphere is maintained; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure is sulfur-tolerant: suitable for a sulfur-containing atmosphere, and has no upper limit for sulfur tolerance; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure has good activity stability: resistant to HCl and other gases that are toxic to the catalyst; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure has high strength, and the particle crushing strength is greater than or equal to 100 N / cm; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure does not use noble metals, the raw materials are cheap and easy to obtain, and the cost is moderate. DETAILED DESCRIPTION

[0051] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0052] It is to be noted that the order of description of the following embodiments is not intended to imply a preference of such order. Additionally, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the present application can exist in a range of forms; it should be understood that the description in a range form is merely for the convenience and brevity, and should not be understood as a rigid limitation to the scope of the present application; therefore, it should be considered that the range description has disclosed all possible sub-ranges and single values in the range. For example, it should be considered that the range description from 1 to 6 has disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single values in the range, such as 1, 2, 3, 4, 5 and 6, regardless of the range. In addition, whenever a numerical range is indicated in this document, it refers to any cited number (fraction or integer) in the indicated range.

[0053] The embodiment of the present application provides a sulfur-tolerant hydrodechlorination catalyst with a core-shell structure, including a carrier and an active component loaded on the carrier.

[0054] The carrier includes a core layer and a shell layer coated outside the core layer.

[0055] The core layer is dodecacalcium heptatitanate with a cage structure.

[0056] The shell layer is titanium dioxide.

[0057] The active elements in the active component include Co and / or Ni and Mo and / or W.

[0058] The sulfur-tolerant hydrodechlorination catalyst with a core-shell structure of the present application takes dodecacalcium heptatitanate (C12A7) with a cage structure as a core, takes titanium dioxide (TiO2) as a shell layer, the C12A7 core is coated by the TiO2, and the active elements in the active component include Co and / or Ni and Mo and / or W. The sulfur-tolerant hydrodechlorination catalyst of the present application is suitable for the hydrodechlorination of organic chlorine in sulfur-containing raw gas coal gas, has the advantages of unique structure, high activity, sulfur tolerance, high strength, good activity stability, moderate cost, etc.

[0059] In some embodiments, the mass fraction of the shell layer in the carrier is 10-25%.

[0060] In some embodiments, the sum of the mass of Co elements and Ni elements is 2-4% of the mass of the carrier, the mass ratio of the Co elements and the Ni elements is (0-1.6):(0-1.6), the sum of the mass of Mo elements and W elements is 4-15% of the mass of the carrier, and the mass ratio of the Mo elements and the W elements is (0-5):(0-5).

[0061] Preferably, the sum of the mass of Co element and Ni element is 2.36-3.96% of the mass of the carrier, the mass ratio of Co element to Ni element is (0-1.57):(0-1.57); the sum of the mass of Mo element and W element is 6.67-10.00% of the mass of the carrier, and the mass ratio of Mo element to W element is (0-5.00):(0-4.26).

[0062] Based on the same inventive concept, the application further provides a preparation method of the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure.

[0063] S1, mixing a Co source and / or a Ni source with a Mo source and / or a W source, adding ammonia water, and stirring to obtain an impregnation solution;

[0064] S2, adding the carrier to the impregnation solution, stirring, and drying to obtain the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure.

[0065] In some embodiments, the carrier is added to the impregnation solution, stirred, and dried at 100-150°C for 2-12 h to obtain the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure.

[0066] In some embodiments, the Co source is cobalt nitrate;

[0067] In some embodiments, the Ni source is nickel nitrate;

[0068] In some embodiments, the Mo source is ammonium heptamolybdate ((NH4)6Mo7O 24 ·4H2O );

[0069] In some embodiments, the W source is ammonium tungstate (ammonium tungsten oxide hydrate, H 26 N6O 40 W 12 ).

[0070] In some embodiments, cobalt nitrate, nickel nitrate, ammonium heptamolybdate, and ammonium tungstate are mixed, ammonia water is added, and stirred to obtain an impregnation solution; the carrier is added to the impregnation solution, stirred, and the impregnated carrier is obtained.

[0071] The mass-volume ratio of cobalt nitrate, nickel nitrate, ammonium heptamolybdate, ammonium tungstate, the carrier, and ammonia water is (0-5) g:(0-5) g:(0-65) g:(0-61) g:(50-60) g:(20-25) mL.

[0072] The ratio of the sum of the mass of cobalt nitrate and nickel nitrate to the mass of the carrier is (3.5-6.5):(50-60).

[0073] The ratio of the sum of the mass of ammonium heptamolybdate and ammonium tungstate to the mass of the carrier is (30-65):(50-60).

[0074] The mass concentration of the ammonia water is 20-30%.

[0075] Preferably, in some embodiments, the mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, the ammonium tungstate, the carrier, and the ammonia water is (0.00-4.83) g:(0.00-4.89) g:(0.00-64.39) g:(0.00-60.14) g:(50-60) g:(20-25) mL.

[0076] The ratio of the sum of the mass of the cobalt nitrate and the nickel nitrate to the mass of the carrier is (3.65-6.07):(50-60).

[0077] The ratio of the sum of the mass of the ammonium heptamolybdate and the ammonium tungstate to the mass of the carrier is (30.05-64.39):(50-60).

[0078] In some embodiments, the cobalt nitrate, the ammonium heptamolybdate, and the ammonia water are mixed to obtain an impregnating solution; the carrier is added to the impregnating solution and stirred to obtain the impregnated carrier; wherein the mass-volume ratio of the cobalt nitrate, the ammonium heptamolybdate, the carrier, and the ammonia water is (1.21-4.83) g:(25.76-64.39) g:(50-60) g:(20-25) mL; and the mass concentration of the ammonia water is 20-30%.

[0079] In some embodiments, the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, and the ammonia water are mixed to obtain an impregnating solution; the carrier is added to the impregnating solution and stirred to obtain the impregnated carrier; wherein the mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, the carrier, and the ammonia water is (1.21-4.83) g:(1.22-4.89) g:(25.76-64.39) g:(50-60) g:(20-25) mL; and the mass concentration of the ammonia water is 20-30%.

[0080] In some embodiments, the cobalt nitrate, the nickel nitrate, the ammonium tungstate, and the ammonia water are mixed to obtain an impregnating solution; the carrier is added to the impregnating solution and stirred to obtain the impregnated carrier; wherein the mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium tungstate, the carrier, and the ammonia water is (1.21-4.83) g:(1.22-4.89) g:(24.06-60.14) g:(50-60) g:(20-25) mL; and the mass concentration of the ammonia water is 20-30%.

[0081] In some embodiments, the cobalt nitrate, nickel nitrate, ammonium heptamolybdate, ammonium tungstate are mixed, then ammonia water is added, and stirring is performed to obtain an impregnation solution; the carrier is added to the impregnation solution, and stirring is performed to obtain the impregnated carrier; wherein the mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, the ammonium tungstate, the carrier, and the ammonia water is (1.21-4.83) g: (1.22-4.89) g: (25.76-64.39) g: (24.06-60.14) g: (50-60) g: (20-25) mL; and the mass concentration of the ammonia water is 20-30%.

[0082] In some embodiments, the cobalt nitrate, nickel nitrate, ammonium heptamolybdate, ammonium tungstate are mixed, then ammonia water is added, and stirring is performed to obtain an impregnation solution; the carrier is added to the impregnation solution, and stirring is performed to obtain the impregnated carrier; wherein the mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, the carrier, and the ammonia water is (1.21-4.83) g: (1.22-4.89) g: (25.76-64.39) g: (50-60) g: (20-25) mL; and the mass concentration of the ammonia water is 20-30%.

[0083] In some embodiments, the cobalt nitrate, nickel nitrate, ammonium heptamolybdate, ammonium tungstate are mixed, then ammonia water is added, and stirring is performed to obtain an impregnation solution; the carrier is added to the impregnation solution, and stirring is performed to obtain the impregnated carrier; wherein the mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, the carrier, and the ammonia water is (1.21-4.83) g: (1.22-4.89) g: (25.76-64.39) g: (50-60) g: (20-25) mL; and the mass concentration of the ammonia water is 20-30%.

[0084] In some embodiments, the cobalt nitrate, nickel nitrate, ammonium heptamolybdate, ammonium tungstate are mixed, then ammonia water is added, and stirring is performed to obtain an impregnation solution; the carrier is added to the impregnation solution, and stirring is performed to obtain the impregnated carrier; wherein the mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, the carrier, and the ammonia water is (1.21-4.83) g: (1.22-4.89) g: (25.76-64.39) g: (50-60) g: (20-25) mL; and the mass concentration of the ammonia water is 20-30%.

[0085] In some embodiments, the cobalt nitrate, nickel nitrate, ammonium heptamolybdate, ammonium tungstate are mixed, then ammonia water is added, and stirring is performed to obtain an impregnation solution; the carrier is added to the impregnation solution, and stirring is performed to obtain the impregnated carrier; wherein the mass-volume ratio of the cobalt nitrate, the nickel nitrate, the ammonium heptamolybdate, the carrier, and the ammonia water is (1.21-4.83) g: (1.22-4.89) g: (25.76-64.39) g: (50-60) g: (20-25) mL; and the mass concentration of the ammonia water is 20-30%.

[0086] In some embodiments, the preparation method of the carrier comprises the following steps:

[0087] S11, preparing twelve calcium aluminates with cage cavity structure;

[0088] S12, mixing the twelve calcium aluminates with cage cavity structure and the titanium source, adding water, kneading to obtain a mixture;

[0089] S13, drying the mixture, and calcining to obtain a carrier.

[0090] In some embodiments, the titanium source is titanium sol; the titanium sol is that nano-titanium dioxide powder (5-20 nm) is dispersed in aqueous medium to form a highly dispersed, homogenized and stabilized transparent liquid.

[0091] In some embodiments, in the step of mixing the twelve calcium aluminates with cage cavity structure and the titanium source, adding water, and kneading, the mass ratio of the twelve calcium aluminates with cage cavity structure, titanium dioxide in the titanium sol, and water is (75-90):(10-25):(40-60);

[0092] In the step of drying the mixture, the drying temperature is 100-150 DEG C, and the drying time is 2-12 h;

[0093] In the step of calcining after drying the mixture, the calcining temperature is 400-500 DEG C, and the calcining time is 2-4 h.

[0094] In some embodiments, since the carrier of the application comprises a core layer and a shell layer coated outside the core layer, the mass fraction of titanium dioxide (TiO2) in the shell layer is 10-25%, the mass fraction of the twelve calcium aluminates with cage cavity structure is 75-90%, and the mass ratio of titanium dioxide (TiO2) and the twelve calcium aluminates with cage cavity structure is (10-25):(75-95). Since titanium dioxide (TiO2) is provided by titanium sol, the mass ratio of titanium dioxide in the twelve calcium aluminates with cage cavity structure, titanium sol, and water is (75-90):(10-25):(40-60).

[0095] In some embodiments, the method for preparing the twelve calcium aluminates with cage cavity structure comprises:

[0096] S21, mixing an aluminum source and a calcium source to obtain a mixed powder;

[0097] S22, adding nitric acid to water to obtain an acid solution;

[0098] S23, adding the mixed powder to the acid solution, and mixing to obtain a wet powder;

[0099] S24, drying the wet powder at 100-150 DEG C for 2-12 h, and calcining at 600-700 DEG C for 2-4 h to obtain the twelve calcium aluminates with cage cavity structure;

[0100] The aluminum source includes aluminum hydroxide and / or pseudo boehmite; in particular, the pseudo boehmite is also known as monohydrate alumina, pseudo one water soft alumina, English name: Pseudo Boehmite, AlOOH.nH2O, n=0.08~0.62;

[0101] The calcium source includes at least one of calcium carbonate, calcium hydroxide, and calcium oxide;

[0102] The molar ratio of aluminum in the aluminum source to calcium in the calcium source is 7:6; in particular, since the chemical formula of dodecacerium aluminate is 12CaO·7Al2O3, the molar ratio of aluminum to calcium is 7:6, so the molar ratio of aluminum in the aluminum source to calcium in the calcium source is 7:6;

[0103] In the step of adding nitric acid to water, the nitric acid is a nitric acid solution with a mass fraction of 65~68%, and the mass ratio of the nitric acid solution to water is (3~5):(48~50);

[0104] In the step of adding nitric acid to water, the molar ratio of aluminum in the aluminum source to water is 1:(2.67~2.78).

[0105] In particular, in some embodiments, after mixing dodecacerium aluminate with a cage cavity structure and a titanium source, water is added, kneaded, and a mixture is obtained; then the mixture is placed in a mold to form a strip shape, and then the strip-shaped mixture is dried and calcined to obtain a carrier.

[0106] The sulfur-resistant hydrogenation dechlorination catalyst with a core-shell structure of the present application is prepared by an impregnation method, the carrier takes C12A7 with a cage cavity structure as the core and TiO2 as the shell, and it is a core-shell structure; C12A7 with a cage cavity structure has abundant micro-channels, which facilitates the diffusion of Cl - 、O 2-Enter, while providing greater reactive surface; TiO2 as a shell, together with the active components to constitute the hydrogenation dechlorination active center; the three have a synergistic effect, that is, it can improve the hydrogenation dechlorination activity, and can maintain the activity stability in the chlorine-containing atmosphere; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure has high activity, and due to the unique core-shell structure, the three have a synergistic effect, that is, it can improve the hydrogenation dechlorination activity, and can maintain the activity stability in the chlorine-containing atmosphere; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure can tolerate sulfur: suitable for a sulfur-containing atmosphere, and has no upper limit for sulfur tolerance; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure has good activity stability: resistant to HCl (HCl is the product of hydrogenation of organic chlorine, so the catalyst of the present application is resistant to HCl) and other gases harmful to the catalyst; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure has high strength, and the particle crushing strength is greater than or equal to 100 N / cm; the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure does not use noble metals, the raw materials are cheap and easy to obtain, and the cost is moderate.

[0107] Based on the same inventive concept, the present application also provides an application of the above-mentioned sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure or the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure prepared by the above-mentioned preparation method in removing organic chlorine in sulfur-containing coal gas.

[0108] In some embodiments, the use conditions of the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure are as follows: the use atmosphere is sulfur-containing coal gas, the reaction temperature is 180-320℃, the space velocity is 500-3000h -1 .

[0109] The sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure and the preparation method and application thereof of the present application are further illustrated in the following specific embodiments. This part further illustrates the content of the present application in combination with specific embodiments, but should not be understood as a limitation of the present application. If not specifically stated, the technical means adopted in the embodiments are conventional means familiar to those skilled in the art. Unless specifically stated, the reagents, methods and equipment adopted in the present application are conventional reagents, methods and equipment in the art.

[0110] Example 1

[0111] The present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure, comprising the following steps:

[0112] S1, mixing 0.85714 mol of calcium hydroxide powder and 1 mol of pseudo-boehmite powder to obtain a mixed powder (the molar ratio of aluminum and calcium in the mixed powder is 7:6);

[0113] S2, 5g of 68% mass concentration nitric acid (nitric acid aqueous solution) is added to 50g (i.e. 2.78mol) of water, and dissolved to obtain a clear transparent solution, which is an acid solution;

[0114] S3, the mixed powder in S1 is added to the acid solution in S2, mixed, to obtain a wet powder material;

[0115] S4, the wet powder material in S3 is dried at 100 DEG C for 12h, and then calcined at 700 DEG C for 2h, to obtain the dodeca calcium heptanium aluminate with cage cavity structure;

[0116] S5, 75g of the dodeca calcium heptanium aluminate with cage cavity structure in S4, and titanium sol (the mass of nano titanium dioxide powder in the titanium sol is 25g, and the average particle size is 15nm) are mixed (it is calculated that the mass ratio of dodeca calcium heptanium aluminate and titanium dioxide is 75:25), 50g of water is added, and kneaded, to obtain a mixture;

[0117] S6, the mixture in S5 is placed in a mold (the mold is a hollow cylindrical body, and the inner diameter is 4mm) to be shaped into a strip-shaped mixture;

[0118] S7, the strip-shaped mixture in S6 is dried at 150 DEG C for 2h, and then calcined at 500 DEG C for 2h, to obtain a carrier;

[0119] S8, 4.83g of cobalt nitrate and 42.93g of ammonium heptamolybdate are mixed, 20mL of ammonia water with a mass concentration of 25% is added, and stirred and dissolved, to obtain an impregnation solution;

[0120] S9, 50g of the carrier in step S7 is added to the impregnation solution in step S8, stirred, placed for 15h, and then dried at 100 DEG C for 12h, to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure.

[0121] Example 2

[0122] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure, which comprises the following steps:

[0123] S1, 0.85714mol of calcium hydroxide powder and 1mol of pseudo-boehmite powder are mixed, to obtain a mixed powder (the molar ratio of aluminum and calcium in the mixed powder is 7:6);

[0124] S2, 5g of nitric acid with a mass concentration of 68% (nitric acid aqueous solution) is added to 50g (2.78mol) of water, and fully dissolved, to obtain a clear and transparent solution, which is an acid solution;

[0125] S3, the mixed powder in S1 is added to the acid solution in S2, mixed, to obtain a wet powder material;

[0126] S4, the wet powder material in S3 is dried at 120 DEG C for 4h, and then calcined at 650 DEG C for 3h, to obtain the dodeca calcium heptanium aluminate with cage cavity structure;

[0127] S5, 85 g of the dodecacalcium heptaluminate with cage structure in S4, titanium sol (the mass of the nano-titanium dioxide powder in the titanium sol is 15 g, and the average particle size is 15 nm) are mixed (it is calculated that the mass ratio of dodecacalcium heptaluminate and titanium dioxide is 85:15 by using this ratio), 50 g of water is added, kneading is performed, and a mixture is obtained;

[0128] S6, the mixture in S5 is placed in a mold (the mold is a hollow cylinder, and the inner diameter is 4 mm) to be formed into a strip-shaped mixture;

[0129] S7, the strip-shaped mixture in S6 is dried at 120 DEG C for 4 h, and then calcined at 450 DEG C for 3 h, so that a carrier is obtained;

[0130] S8, 2.41 g of cobalt nitrate, 2.45 g of nickel nitrate, and 42.93 g of ammonium heptamolybdate are mixed, 20 mL of ammonia water with a mass concentration of 25% is added, stirring is performed to dissolve, and an impregnation solution is obtained;

[0131] S9, 50 g of the carrier in step S7 is added to the impregnation solution in step S8, stirring is performed, and then placed for 15 h, and then dried at 120 DEG C for 4 h, so that a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure is obtained.

[0132] Example 3

[0133] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure, which comprises the following steps:

[0134] S1, 0.85714 mol of calcium hydroxide powder and 1 mol of pseudo-boehmite powder are mixed to obtain a mixed powder (the molar ratio of aluminum and calcium in the mixed powder is 7:6);

[0135] S2, 5 g of nitric acid with a mass concentration of 68% (nitric acid aqueous solution) is added to 50 g (2.78 mol) of water, and fully dissolved to obtain a clear and transparent solution, which is an acid solution;

[0136] S3, the mixed powder in S1 is added to the acid solution in S2, and mixed to obtain a wet powder;

[0137] S4, the wet powder in S3 is dried at 150 DEG C for 2 h, and then calcined at 600 DEG C for 4 h, so that dodecacalcium heptaluminate with a cage structure is obtained;

[0138] S5, 90 g of the dodecacalcium heptaluminate with a cage structure in S4, titanium sol (the mass of the nano-titanium dioxide powder in the titanium sol is 10 g, and the average particle size is 15 nm) are mixed (it is calculated that the mass ratio of dodecacalcium heptaluminate and titanium dioxide is 90:10 by using this ratio), 50 g of water is added, kneading is performed, and a mixture is obtained;

[0139] S6, the mixture in S5 is placed in a mold (the mold is a hollow cylindrical shape with an inner diameter of 4 mm) to form a strip-shaped mixture;

[0140] S7, the strip-shaped mixture in S6 is dried at 100°C for 12h, and then calcined at 400°C for 4h to obtain the carrier;

[0141] S8, 2.41g of cobalt nitrate, 2.45g of nickel nitrate and 60.14g of ammonium tungstate are mixed, then 20mL of 25% ammonia water is added, and the mixture is stirred and dissolved to obtain an impregnation solution;

[0142] S9, 50g of the carrier in step S7 is added to the impregnation solution in step S8, stirred, placed for 15h, and then dried at 150°C for 2h to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure.

[0143] Example 4

[0144] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure, comprising the following steps:

[0145] S1, 0.85714mol of calcium hydroxide powder and 1mol of pseudo-boehmite powder are mixed to obtain a mixed powder (the molar ratio of aluminum to calcium in the mixed powder is 7:6);

[0146] S2, 5g of 68% nitric acid (nitric acid aqueous solution) is added to 50g (i.e. 2.78mol) of water, and the mixture is fully dissolved to obtain a clear and transparent solution, which is an acid solution;

[0147] S3, the mixed powder in S1 is added to the acid solution in S2, and the mixture is mixed to obtain a wet powder;

[0148] S4, the wet powder in S3 is dried at 150°C for 2h, and then calcined at 600°C for 4h to obtain dodecacalcium heptanium with a cage structure;

[0149] S5, 90g of dodecacalcium heptanium with a cage structure in S4 and titanium sol (the mass of nano-titanium dioxide powder in the titanium sol is 10g, and the average particle size is 15nm) are mixed (it is calculated that the mass ratio of dodecacalcium heptanium to titanium dioxide is 90:10 by using this ratio), then 50g of water is added, and the mixture is kneaded to obtain a mixture;

[0150] S6, the mixture in S5 is placed in a mold (the mold is a hollow cylindrical shape with an inner diameter of 4 mm) to form a strip-shaped mixture;

[0151] S7, the strip-shaped mixture in S6 is dried at 100°C for 12h, and then calcined at 400°C for 4h to obtain the carrier;

[0152] S8, 2.41 g of cobalt nitrate, 2.45 g of nickel nitrate, 25.76 g of ammonium heptamolybdate, 24.06 g of ammonium tungstate were mixed, 20 mL of ammonia water with a mass concentration of 25% was added, and stirring and dissolution were performed to obtain an impregnation solution;

[0153] S9, 50 g of the carrier in step S7 was added to the impregnation solution in step S8, stirring was performed, and then standing for 15 h, and drying at 150 DEG C for 2 h to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure.

[0154] Example 5

[0155] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure, comprising the following steps:

[0156] S1, 0.85714 mol of calcium hydroxide powder and 1 mol of pseudo-boehmite powder were mixed to obtain a mixed powder (the molar ratio of aluminum and calcium in the mixed powder was 7:6);

[0157] S2, 5 g of nitric acid with a mass concentration of 68% (nitric acid aqueous solution) was added to 50 g (2.78 mol) of water, and the nitric acid was dissolved to obtain a clear and transparent solution, that is, an acid solution;

[0158] S3, the mixed powder in S1 was added to the acid solution in S2, and mixing was performed to obtain a wet powder;

[0159] S4, the wet powder in S3 was dried at 120 DEG C for 4 h, and then calcined at 650 DEG C for 3 h to obtain dodecacalcium aluminophosphate with a cage structure;

[0160] S5, 85 g of dodecacalcium aluminophosphate with a cage structure in S4, and titanium sol (the mass of nano-titanium dioxide powder in the titanium sol was 20 g, and the average particle size was 15 nm) were mixed (it was calculated that the mass ratio of dodecacalcium aluminophosphate and titanium dioxide was 85:20), 50 g of water was added, and kneading was performed to obtain a mixture;

[0161] S6, the mixture in S5 was placed in a mold (the mold was a hollow cylindrical body, and the inner diameter was 4 mm) to be formed into a strip-shaped mixture;

[0162] S7, the strip-shaped mixture in S6 was dried at 120 DEG C for 4 h, and then calcined at 450 DEG C for 3 h to obtain a carrier;

[0163] S8, 2.41 g of cobalt nitrate, 2.45 g of nickel nitrate, 25.76 g of ammonium heptamolybdate, 24.06 g of ammonium tungstate were mixed, 20 mL of ammonia water with a mass concentration of 25% was added, and stirring and dissolution were performed to obtain an impregnation solution;

[0164] S9, 50g of the carrier in step S7 is added into the impregnation solution in step S8, after stirring, placed for 15h, and dried at 120℃ for 4h, to obtain the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure.

[0165] Example 6

[0166] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure, comprising the following steps:

[0167] S1, 0.85714mol of calcium hydroxide powder and 1mol of pseudo-boehmite powder are mixed to obtain a mixed powder (the molar ratio of aluminum and calcium in the mixed powder is 7:6);

[0168] S2, 5g of 68% mass concentration nitric acid (nitric acid aqueous solution) is added into 50g (2.78mol) of water, and is fully dissolved to obtain a clear and transparent solution, that is, an acid solution;

[0169] S3, the mixed powder in S1 is added into the acid solution in S2, and is mixed to obtain a wet powder material;

[0170] S4, the wet powder material in S3 is dried at 120℃ for 4h, and is calcined at 650℃ for 3h, to obtain dodecacalcium heptatitanate with cage structure;

[0171] S5, 85g of dodecacalcium heptatitanate with cage structure in S4, and titanium sol (the mass of nano-titanium dioxide powder in the titanium sol is 20g, and the average particle size is 15nm) are mixed (it is calculated that the mass ratio of dodecacalcium heptatitanate and titanium dioxide is 85:20 in this proportion), 50g of water is added, and kneading is performed, to obtain a mixture;

[0172] S6, the mixture in S5 is placed in a mold (the mold is a hollow cylindrical body, and the inner diameter is 4mm) to be formed into a strip-shaped mixture;

[0173] S7, the strip-shaped mixture in S6 is dried at 120℃ for 4h, and is calcined at 450℃ for 3h, to obtain a carrier;

[0174] S8, 4.83g of cobalt nitrate and 42.93g of ammonium molybdate are mixed, 20mL of 25% mass concentration ammonia water is added, stirring is performed, and an impregnation solution is obtained;

[0175] S9, 50g of the carrier in step S7 is added into the impregnation solution in step S8, after stirring, placed for 15h, and dried at 120℃ for 4h, to obtain the sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure.

[0176] Example 7

[0177] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure, comprising the following steps:

[0178] S1, 0.85714 mol of calcium hydroxide powder and 1 mol of pseudo-boehmite powder are mixed to obtain a mixed powder (the molar ratio of aluminum and calcium in the mixed powder is 7:6);

[0179] S2, 5g of 68% mass concentration nitric acid (nitric acid aqueous solution) is added into 50g (2.78mol) of water, and is fully dissolved to obtain a clear and transparent solution, that is, an acid solution;

[0180] S3, the mixed powder in S1 is added into the acid solution in S2, and is mixed to obtain a wet powder material;

[0181] S4, the wet powder material in S3 is dried at 120 DEG C for 4h, and is calcined at 650 DEG C for 3h, so that twelve calcium heptanium acid with a cage cavity structure is obtained;

[0182] S5, 85g of the twelve calcium heptanium acid with a cage cavity structure in S4 and titanium sol (the mass of nano-titanium dioxide powder in the titanium sol is 20g, and the average particle size is 15nm) are mixed (it is calculated that the mass ratio of the twelve calcium heptanium acid and the titanium dioxide is 85:20), 50g of water is added, and kneading is performed, so that a mixture is obtained;

[0183] S6, the mixture in S5 is placed in a mold (the mold is a hollow cylindrical body, and the inner diameter is 4mm) to be formed into a strip-shaped mixture;

[0184] S7, the strip-shaped mixture in S6 is dried at 120 DEG C for 4h, and is calcined at 450 DEG C for 3h, so that a carrier is obtained;

[0185] S8, 4.89g of nickel nitrate and 42.93g of ammonium heptamolybdate are mixed, 20mL of 25% mass concentration ammonia water is added, stirring and dissolving are performed, so that an impregnation solution is obtained;

[0186] S9, 50g of the carrier in the step S7 is added into the impregnation solution in the step S8, stirring is performed, then 15h is placed, and then drying is performed at 120 DEG C for 4h, so that a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure is obtained.

[0187] Example 8

[0188] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure, comprising the following steps:

[0189] S1, 0.85714 mol of calcium hydroxide powder and 1 mol of pseudo-boehmite powder are mixed to obtain a mixed powder (the molar ratio of aluminum and calcium in the mixed powder is 7:6);

[0190] S2, 5g of nitric acid with a mass concentration of 68% (nitric acid aqueous solution) is added to 50g (i.e. 2.78mol) of water, and is fully dissolved to obtain a clear transparent solution, which is an acid solution;

[0191] S3, the mixed powder in S1 is added to the acid solution in S2, and is mixed to obtain wet powder material;

[0192] S4, the wet powder material in S3 is dried at 120℃ for 4h, and is calcined at 650℃ for 3h, to obtain twelve calcium aluminates with cage cavity structure;

[0193] S5, 85g of twelve calcium aluminates with cage cavity structure in S4 and titanium sol (the mass of nano-titanium dioxide powder in the titanium sol is 20g, and the average particle size is 15nm) are mixed (it is calculated that the mass ratio of the twelve calcium aluminates and the titanium dioxide is 85:20), 50g of water is added, and kneading is performed, to obtain a mixture;

[0194] S6, the mixture in S5 is placed in a mold (the mold is a hollow cylindrical body with an inner diameter of 4mm) to be formed into a strip-shaped mixture;

[0195] S7, the strip-shaped mixture in S6 is dried at 120℃ for 4h, and is calcined at 450℃ for 3h, to obtain a carrier;

[0196] S8, 2.41g of cobalt nitrate, 1.22g of nickel nitrate and 64.39g of ammonium molybdate are mixed, 22mL of ammonia water with a mass concentration of 25% is added, and stirring is performed to obtain an impregnation solution;

[0197] S9, 50g of the carrier in step S7 is added to the impregnation solution in step S8, stirring is performed, and then the mixture is placed for 15h, and is dried at 120℃ for 4h, to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure.

[0198] Example 9

[0199] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure, which comprises the following steps:

[0200] S1, 0.85714mol of calcium hydroxide powder and 1mol of pseudo-boehmite powder are mixed to obtain mixed powder (the molar ratio of aluminum and calcium in the mixed powder is 7:6);

[0201] S2, 5g of nitric acid with a mass concentration of 68% (nitric acid aqueous solution) is added to 50g (i.e. 2.78mol) of water, and is fully dissolved to obtain a clear transparent solution, which is an acid solution;

[0202] S3, the mixed powder in S1 is added to the acid solution in S2, and is mixed to obtain wet powder material;

[0203] S4, drying the wet powder in S3 at 120 DEG C for 4h, and then calcining at 650 DEG C for 3h to obtain dodecacalcium heptanium with cage structure;

[0204] S5, mixing 85g of dodecacalcium heptanium with cage structure in S4 and titanium sol (the mass of nano-titanium dioxide powder in the titanium sol is 20g, and the average particle size is 15nm), adding 50g of water, and kneading to obtain a mixture;

[0205] S6, placing the mixture in S5 in a mold (the mold is a hollow cylindrical body with an inner diameter of 4mm) to form a strip-shaped mixture;

[0206] S7, drying the strip-shaped mixture in S6 at 120 DEG C for 4h, and then calcining at 450 DEG C for 3h to obtain a carrier;

[0207] S8, mixing 3.62g of cobalt nitrate, 2.45g of nickel nitrate, and 30.05g of ammonium heptamolybdate, adding 20mL of 25% ammonia water, and stirring to dissolve to obtain an impregnation solution;

[0208] S9, adding 50g of the carrier in step S7 to the impregnation solution in step S8, stirring, placing for 15h, and then drying at 120 DEG C for 4h to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure.

[0209] Example 10

[0210] The embodiment of the present application provides a preparation method of a sulfur-tolerant hydrogenation dechlorination catalyst with core-shell structure, which comprises the following steps:

[0211] S1, mixing 0.85714mol of calcium hydroxide powder and 1mol of pseudo-boehmite powder to obtain a mixed powder (the molar ratio of aluminum to calcium in the mixed powder is 7:6);

[0212] S2, adding 5g of 68% nitric acid (nitric acid aqueous solution) to 50g (2.78mol) of water, and fully dissolving to obtain a clear and transparent solution, which is an acid solution;

[0213] S3, adding the mixed powder in S1 to the acid solution in S2, and mixing to obtain a wet powder;

[0214] S4, drying the wet powder in S3 at 120 DEG C for 4h, and then calcining at 650 DEG C for 3h to obtain dodecacalcium heptanium with cage structure;

[0215] S5, 85 g of the mixture of the dodecacalcium heptaluminate with the cage structure in S4, and the titanium sol (the mass of the nano-titanium dioxide powder in the titanium sol is 20 g, and the average particle size is 15 nm) were mixed (it was calculated that the mass ratio of the dodecacalcium heptaluminate and the titanium dioxide was 85:20), 50 g of water was added, kneading was performed, and a mixture was obtained;

[0216] S6, the mixture in S5 was placed in a mold (the mold was a hollow cylinder, and the inner diameter was 4 mm) to be formed into a strip-shaped mixture;

[0217] S7, the strip-shaped mixture in S6 was dried at 120 DEG C for 4 h, and then calcined at 450 DEG C for 3 h, to obtain a carrier;

[0218] S8, 1.21 g of cobalt nitrate, 2.45 g of nickel nitrate, and 64.39 g of ammonium heptamolybdate were mixed, 22 mL of ammonia water with a mass concentration of 25% was added, and stirring was performed to obtain an impregnation solution;

[0219] S9, 50 g of the carrier in step S7 was added to the impregnation solution in step S8, stirring was performed, and then the mixture was placed for 15 h, and then dried at 120 DEG C for 4 h, to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure.

[0220] Comparative Example 1

[0221] The present comparative example discloses a hydrogenation dechlorination catalyst and a preparation method thereof, which comprises the following steps:

[0222] S1, 118 g of pseudo-boehmite was mixed with 2 g of sesbania powder and 100 g of dilute nitric acid with a concentration of 5 wt% to obtain a paste, and then the paste was extruded into a strip, and then dried at 120 DEG C for 8 h and calcined at 530 DEG C for 7 h to obtain a catalyst carrier;

[0223] S2, 43 g of ammonium heptamolybdate and 21 g of nickel nitrate were added to 150 mL of deionized water to obtain an active metal impregnation solution, and then 100 g of the above carrier was saturatedly impregnated in the impregnation solution for 10 h, and finally dried at 135 DEG C for 5 h and calcined at 520 DEG C for 6 h to obtain a catalyst semi-product containing Ni and Mo active metals;

[0224] S3, 6.6 g of ammonium dihydrogen phosphate was added to 90 mL of deionized water to obtain an auxiliary impregnation solution, and then 100 g of the above catalyst semi-product was saturatedly impregnated in the impregnation solution for 6 h, and finally dried at 150 DEG C for 7 h and calcined at 540 DEG C for 6.5 h to obtain a hydrogenation dechlorination catalyst containing 4.8 wt% of nickel oxide, 25.0 wt% of molybdenum oxide, and 3.0 wt% of phosphorus oxide.

[0225] Performance test

[0226] The activity and strength of the sulfur-tolerant hydrogenation dechlorination catalysts with core-shell structure prepared in Examples 1-10 and the hydrogenation dechlorination catalyst prepared in Comparative Example 1 were tested.

[0227] The catalyst strength was measured on an intelligent strength instrument, and the lateral pressure strength was used as the index.

[0228] The hydrogenation dechlorination performance test was carried out in a 28 mm diameter quartz glass reaction tube. The sulfur-tolerant hydrogenation dechlorination catalysts with core-shell structure prepared in Examples 1-10 and the hydrogenation dechlorination catalyst prepared in Comparative Example 1 were cut into particles with a height-diameter ratio of about 1 (specifically, the catalyst was cut into a cylindrical shape with a diameter of 4 mm and a height of 4 mm), and then were respectively placed in the quartz glass reaction tube. The gas was simulated coal gas, and the main components (v / v) were as follows: 18% CO, 20% H2, 9% CO2, 100 ppm CH2Cl2, and 500 ppm H2S. The balance was N2 (i.e., the volume concentration of CO in the simulated coal gas was 18%, the volume concentration of H2 was 20%, the volume concentration of CO2 was 9%, the volume concentration of CH2Cl2 was 0.01%, the volume concentration of H2S was 0.05%, and the balance was N2); the volume space velocity was 2000 h-1; the reaction temperature was 200°C; the reaction pressure was 0.8 MPa; and the activity was expressed by the CH2Cl2 conversion rate (hydrogenation dechlorination reaction formula: CH2Cl2+2H2=CH4+2HCl). Before the evaluation, the catalysts were pre-sulfided according to HG / T 2780-2016. The test results are shown in Table 1. -1

[0229] Table 1- Hydrogenation dechlorination activity test results of different catalysts

[0230]

[0231] As can be seen from Table 1, the CH2Cl2 conversion rate of the sulfur-tolerant hydrogenation dechlorination catalysts in Examples 1-10 was significantly higher than that of the hydrogenation dechlorination catalyst in Comparative Example 1, and all of them showed very high activity (>95%), with the highest activity reaching 99.8% (Example 5). With the increase of the amount of added titanium dioxide, the compressive strength gradually increased, showing a significant correlation. With the increase of the loading amount of the active component, the compressive strength also showed a gradually increasing trend. It is well known that increasing the compressive strength is beneficial to reducing the resistance of the catalyst bed in industrial production, reducing the power consumption in industrial production, and prolonging the service life of the catalyst. The above data show that the catalyst and the preparation method thereof proposed in the present application have significant advantages.

[0232] The above description is only the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.​

Claims

1. A sulfur-tolerant hydrodechlorination catalyst having a core-shell structure, characterized in that, The active component is loaded on the carrier. The carrier comprises a core layer and a shell layer coated on the core layer. The core layer is dodecacalcium heptatitanate with a cage structure. The shell layer is titanium dioxide. The active element in the active component comprises a first component and a second component. The first component is Co and / or Ni, and the second component is Mo and / or W.

2. The sulfur-tolerant hydrodechlorination catalyst with core-shell structure according to claim 1, wherein the core is composed of a transition metal oxide and the shell is composed of a transition metal sulfide. The mass fraction of the shell layer in the carrier is 10-25%. The sum of the mass of Co and Ni is 2-4% of the mass of the carrier, and the mass ratio of Co to Ni is (0-1.6):(0-1.6).

3. A process for producing a sulfur-tolerant hydrodechlorination catalyst having a core-shell structure according to any one of claims 1 to 2, characterized by, The sum of the mass of Mo and W is 4-15% of the mass of the carrier, and the mass ratio of Mo to W is (0-5):(0-5). The amounts of Co, Ni, Mo and W cannot be all zero. The method comprises the following steps:

4. The method for preparing a sulfur-tolerant hydrodechlorination catalyst having a core-shell structure according to claim 3, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, zirconium oxide, hafnium oxide, and cerium oxide. The first component source and the second component source are mixed, then ammonia is added, and stirring is performed to obtain an impregnation solution.

5. The method for preparing a sulfur-tolerant hydrodechlorination catalyst having a core-shell structure according to claim 3, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, zirconium oxide, hafnium oxide, and cerium oxide. The first component source is a Co source and / or a Ni source, and the second component source is a Mo source and / or a W source. The carrier is added to the impregnation solution, stirring is performed, and then drying is performed to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure. The carrier is added to the impregnation solution, stirring is performed, and then drying is performed at 100-150°C for 2-12 hours to obtain a sulfur-tolerant hydrogenation dechlorination catalyst with a core-shell structure. The Co source is cobalt nitrate.

6. The method for preparing a sulfur-tolerant hydrodechlorination catalyst having a core-shell structure according to claim 5, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, zirconium oxide, hafnium oxide, and cerium oxide. The Ni source is nickel nitrate. The Mo source is ammonium heptamolybdate. The W source is ammonium tungstate. The first component source and the second component source are mixed, then ammonia is added, and stirring is performed to obtain an impregnation solution. The first component source is cobalt nitrate and / or nickel nitrate, and the second component source is ammonium heptamolybdate and / or ammonium tungstate.

7. The method for preparing a sulfur-tolerant hydrodechlorination catalyst having a core-shell structure according to claim 3, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, zirconium oxide, hafnium oxide, and cerium oxide. The mass-volume ratio of the cobalt nitrate, nickel nitrate, ammonium heptamolybdate, ammonium tungstate, carrier and ammonia is (0-5)g:(0-5)g:(0-65)g:(0-61)g:(50-60)g:(20-25)mL. The amounts of cobalt nitrate, nickel nitrate, ammonium heptamolybdate and ammonium tungstate cannot be all zero. The ratio of the sum of the mass of cobalt nitrate and nickel nitrate to the mass of the carrier is (3.5-6.5):(50-60). The ratio of the sum of the mass of ammonium heptamolybdate and ammonium tungstate to the mass of the carrier is (30-65):(50-60).

8. The method for preparing a sulfur-tolerant hydrodechlorination catalyst having a core-shell structure according to claim 7, wherein the metal oxide is at least one selected from the group consisting of titanium oxide, zirconium oxide, hafnium oxide, and cerium oxide. The mass concentration of the ammonia is 20-30%. The preparation method of the carrier comprises the following steps: Dodecacalcium heptatitanate with a cage structure is prepared. Dodecacalcium heptatitanate with a cage structure and a titanium source are mixed, then water is added, and kneading is performed to obtain a mixture. The mixture is dried, and then calcination is performed to obtain the carrier. The titanium source is titanium sol. In the step of mixing dodecacalcium heptatitanate with a cage structure and a titanium source, and then adding water and kneading, the mass ratio of dodecacalcium heptatitanate with a cage structure, titanium dioxide and water is (75-90):(10-25):(40-60). In the step of drying the mixture, the drying temperature is 100-150°C, and the drying time is 2-12 hours. In the step of drying and calcining the mixture, the calcining temperature is 400-500℃, and the calcining time is 2-4h; The preparation method of the twelve calcium dodecacalcium aluminates with cage cavity structure comprises the following steps: Mixing an aluminum source and a calcium source to obtain a mixed powder; Adding nitric acid into water to obtain an acid solution; Adding the mixed powder into the acid solution and mixing to obtain a wet powder material; Drying the wet powder material at 100-150℃ for 2-12h, and then calcining at 600-700℃ for 2-4h to obtain the twelve calcium dodecacalcium aluminates with cage cavity structure; The aluminum source comprises aluminum hydroxide and / or pseudo-boehmite; The calcium source comprises at least one of calcium carbonate, calcium hydroxide and calcium oxide; The molar ratio of aluminum in the aluminum source to calcium in the calcium source is 7:6; In the step of adding nitric acid into water, the nitric acid is a nitric acid solution with a mass fraction of 65-68%, and the mass ratio of the nitric acid solution to water is (3-5):(48-50). In the steps of mixing the aluminum source and the calcium source to obtain the mixed powder and adding nitric acid into water, the molar ratio of aluminum in the aluminum source to water is 1:(2.67-2.78).

9. Use of the sulfur-tolerant hydrodechlorination catalyst with core-shell structure according to any one of claims 1-2 or prepared by the preparation method according to any one of claims 3-8 in removing organic chlorine in sulfur-containing coal gas.

10. The use according to claim 9, wherein the sulfur-tolerant hydrodechlorination catalyst having a core-shell structure is used under the conditions of a sulfur-containing coal gas as a use atmosphere, a reaction temperature of 180 to 320°C, and a space velocity of 500 to 3000 h"1. -1 .

Images