An industrial gas purification catalyst and its preparation and use

Abstract

The present application belongs to the field of catalysts, and relates to an industrial gas purification catalyst and preparation and application thereof. The industrial gas purification catalyst comprises A-type molecular sieve, MoO3 / WO3 and NiO / CoO supported on the A-type molecular sieve, the content of molybdenum or tungsten is 3-12 wt% based on MoO3 or WO3, the content of nickel or cobalt is 3-7 wt% based on NiO or CoO, and the molecular sieve further contains 55-75% of alkali metal or alkaline earth metal which is not ion-exchanged away in terms of molar ratio, and the alkali metal or alkaline earth metal is sodium, potassium or calcium. The catalyst can be used for purification of oxygen, olefin, HCN and thiophene, disulfide, mercaptan, sulfide, CS2 and / or COS in a gas source containing ammonia and high CO+CO2, so as to achieve a target purification effect.

Description

Technical Field

[0001] The present invention relates to the field of catalysts, and in particular to an industrial gas purification catalyst and a preparation method thereof. The catalyst is suitable for catalytically purifying oxygen, olefins, HCN and complex sulfides in industrial gases containing ammonia and high CO+CO2, such as coal gas, blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, calcium carbide tail gas and other industrial waste gases. Background Art

[0002] In recent years, domestic coal chemical industry has developed rapidly, and the products produced have greatly surpassed the traditional synthetic ammonia, urea and methanol. In many cases, the raw coal gas from the gasifier no longer needs to be converted and is directly washed with low-temperature methanol and deep-cold separated in a cold box to extract CO and H2 in the coal gas to produce different chemical products. The unconverted raw coal gas contains impurities such as oxygen, olefins, HCN and complex sulfides, which need to be purified before entering the low-temperature methanol washing and cold box to remove oxygen, saturate olefins, convert HCN into NH3, and convert complex sulfides into hydrogen sulfide.

[0003] In addition, the comprehensive utilization of blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas and calcium carbide tail gas has become a new trend. In addition to useful components such as CH4, CO and H2, these industrial waste gases also contain impurities such as oxygen, olefins, HCN and complex sulfides that need to be purified.

[0004] Hydrogenation treatment of impurities such as oxygen, olefins, HCN, thiophene, disulfide, mercaptan, sulfide and carbon disulfide is a conventional and effective purification method. At the same time, cobalt-molybdenum hydrogenation catalysts have also been widely and successfully used in the natural gas industry. However, industrial waste gases such as crude coal gas, blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, and calcium carbide tail gas are different from natural gas. They contain high contents of CO and CO2. When the cobalt-molybdenum hydrogenation catalyst is used at a temperature greater than 230°C, the high contents of CO and CO2 will react with the H2 in the gas source to produce the following side reactions:

[0005] CO disproportionation reaction: 2CO==C(S)+CO2 (1)

[0006] CO reduction reaction: CO + H2 == C(S) + H2O (2)

[0007] CO methanation reaction: CO + 3H2 = = CH4 + H2O (3)

[0008] CO2 methanation reaction: CO2+4H2==CH4+2H2O(4)

[0009] Side reactions (1) and (2) will cause the catalyst to be deactivated by carbon deposition. Side reactions (3) and (4) are highly exothermic reactions, which will cause the catalyst bed to overheat. Overheating of the bed will aggravate the catalyst deactivation by carbon deposition. There have been many cases of dangerous accidents such as overheating and reactor burning caused by the use of purifiers in gas sources containing CO, CO2 and H2 under high temperature conditions. Therefore, the cobalt-molybdenum catalyst traditionally widely used in the hydrodesulfurization and deolefination of natural gas cannot be used for hydrogenation purification of crude coal gas and industrial gases such as blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, and calcium carbide tail gas. Currently, the hydrogenation catalysts sold on the market at home and abroad all require CO+CO2≤10%. The market is in urgent need of a hydrogenation catalyst that can be used in high-content CO+CO2 working conditions.

[0010] At the same time, industrial gases such as raw coal gas, blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, and calcium carbide tail gas contain tens to thousands of ppm of NH3. The existing catalysts for hydrogenation treatment of impurities such as oxygen, olefins, HCN, thiophene, disulfide, mercaptan, sulfide and carbon disulfide require inlet ammonia <0.1ppm. They are quickly deactivated when used under conditions where ammonia exceeds the standard. In order to simplify the process, the market urgently needs hydrogenation catalysts that can be used in ammonia-containing conditions.

[0011] In addition, transition metal-containing catalysts can also undergo varying degrees of FT reaction under high temperature conditions, generating a certain amount of multi-carbon chain macromolecular hydrocarbon substances, which not only increases raw material consumption and affects the normal operation of downstream PSA, low-temperature methanol washing and cold box, but also easily blocks the catalyst pores and causes carbon deposits, which should be avoided as much as possible. Summary of the Invention

[0012] The present invention addresses the shortcomings of existing technologies by providing an industrial gas purification catalyst and its preparation. The catalyst can be used to purify oxygen, olefins, HCN, and complex sulfides such as thiophene, disulfide, mercaptan, sulfide, CS2, and COS from ammonia-containing and high-CO+CO2 source gases, achieving the desired purification effect.

[0013] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0014] Provided is an industrial gas purification catalyst, comprising a type A molecular sieve and MoO3 / WO3 (MoO3 or WO3) and NiO / CoO (NiO or CoO) supported on the type A molecular sieve, wherein the content of molybdenum or tungsten is 3-12wt% based on MoO3 or WO3, and the content of nickel or cobalt is 3-7wt% based on NiO or CoO. The molecular sieve also contains 55%-75% by molar ratio of alkali metal or alkaline earth metal that has not been ion-exchanged, wherein the alkali metal or alkaline earth metal is sodium, potassium or calcium.

[0015] According to the above scheme, the sieve size of type A molecular sieve is

[0016] According to the above scheme, the type A molecular sieve can be commercially available 3A, 4A, or 5A molecular sieves.

[0017] Typical chemical composition of type A molecular sieve: Wherein M represents Na, K, and Ca.

[0018] Typical chemical composition of 3A molecular sieve: Typical chemical composition of 4A molecular sieve: Typical chemical composition of 5A molecular sieve:

[0019] According to the above scheme, the industrial gas purification catalyst is firstly to pass the A type molecular sieve through NH4 + Ion exchange, roasting to remove ammonia, and then ion exchange loading Ni / Co, so that the molecular sieve still contains 55% to 75% of alkali metal or alkaline earth metal that has not been ion exchanged, the alkali metal or alkaline earth metal is sodium, potassium, and calcium, and then loaded with Mo / W to obtain.

[0020] According to the above scheme, the preparation method of the above industrial gas purification catalyst specifically includes the following steps:

[0021] (1) ion exchange the type A molecular sieve with an ammonium salt solution at 80-100°C for 3-10 hours, repeat the exchange multiple times, filter, wash, and then calcine at 300-400°C for use;

[0022] (2) preparing a solution containing Ni / Co, stirring the solution with the powder obtained in step (1) at 80-100° C. for 5-8 hours, repeating the exchange multiple times, filtering, washing, and drying for later use;

[0023] (3) preparing a solution containing the active component Mo / W, impregnating an equal amount of the solution onto the powder obtained in step (2), and drying the solution for later use;

[0024] (4) Adding a binder to the powder obtained in step (3) and shaping it into a spherical, bar-shaped or columnar shape, and activating it at 400-600°C to complete the catalyst preparation.

[0025] According to the above scheme, after the ion exchange in steps (1) and (2), it is ensured that the molecular sieve still contains alkali metals and alkaline earth metals such as sodium, potassium, and calcium that have not been ion-exchanged in a molar ratio of 55% to 75%.

[0026] According to the above scheme, the ammonium salt includes but is not limited to ammonium chloride, ammonium sulfate, and ammonium nitrate.

[0027] According to the above scheme, the active components in the solution containing the active components Mo / W and Ni / Co are all salts thereof, including but not limited to ammonium molybdate, ammonium metatungstate, nickel nitrate, and cobalt nitrate.

[0028] According to the above scheme, as needed, ammonia water can be used as a co-solvent in the preparation of the solution of the active component Mo / W to prepare the solution of the active component salt.

[0029] According to the above scheme, the shaped dosage form can be spherical, bar-shaped or column-shaped.

[0030] A second aspect of the present invention provides the use of the above-mentioned industrial gas purification catalyst for catalytic purification of industrial gases containing ammonia and high CO+CO2 source oxygen, olefins, HCN, and complex sulfides. Furthermore, the operating temperature is 230-450°C, and the complex sulfides include thiophene, disulfide, mercaptans, sulfides, CS2, and other complex sulfides.

[0031] Furthermore, the industrial gas purification catalyst of the present invention can also be used for the removal of COS, and the COS removal temperature is 80-200°C.

[0032] Preferably, oxygen, olefins, HCN, thiophene, disulfide, mercaptan, sulfide, CS2 and other complex sulfide impurities in the gas source are purified into water, saturated hydrocarbons, ammonia and H2S at 230-450°C, and then COS impurities are purified into H2S at 80-200°C. In this process, CO conversion and its reverse reaction do not occur, and side reactions such as CO disproportionation and methanation are greatly reduced, and no new C m H n (m≥3) and other hydrocarbon substances.

[0033] Furthermore, the ammonia- and high-CO+CO2-rich gas source is an industrial gas such as raw coal gas, blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, or calcium carbide tail gas, with an NH3 content of 0.001% to 0.5% and a CO+CO2 content greater than 10%. The ammonia- and high-CO+CO2-rich gas source generally also contains H2. If necessary, hydrogen can be added to the gas source.

[0034] Traditional cobalt-molybdenum hydrogenation catalysts used in natural gas chemical industry use activated alumina carriers. In order to hydrogenate and purify oxygen, olefins, and complex sulfides such as thiophene, mercaptans, and disulfides, they must be used above 350°C. However, when the system contains a high CO+CO2 gas source, side reactions such as methanation and CO disproportionation at temperatures exceeding 230°C can easily lead to catalyst overheating, carbon deposition, and deactivation, and even burn the catalyst and reactor, resulting in safety accidents. At the same time, the FT reaction occurs to generate multi-carbon chain macromolecular hydrocarbons, which not only increases raw material consumption and affects the normal operation of downstream PSA, low-temperature methanol washing, and cold box, but also easily blocks the catalyst pores and causes carbon deposition.

[0035] The industrial gas purification catalyst of the present invention can be applied to industrial gases containing NH3 and high CO+CO2, such as crude coal gas, blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, calcium carbide tail gas and other industrial waste gases. It purifies oxygen, olefins, HCN and thiophene, disulfide, mercaptan, sulfide, CS2 and other complex sulfide impurities in the gas source into water, saturated hydrocarbons, ammonia and H2S at 230-450°C, and purifies COS impurities into H2S at 80-200°C. At the same time, CO conversion and its reverse reaction do not occur, and side reactions such as CO disproportionation and methanation are greatly reduced. No new C m H n (m≥3) and other hydrocarbon substances.

[0036] The industrial gas purification catalyst of the present invention is used after sulfurization. It is used to purify oxygen, olefins, HCN, and complex sulfides such as thiophene, disulfide, mercaptan, sulfide, CS2, and / or COS. The removal rates for oxygen, olefins, mercaptan, sulfide, disulfide, and CS2 are >95%, and the removal rates for HCN, COS, and thiophene are >90%.

[0037] The reactions involved are as follows:

[0038] O2+2H2==2H2O

[0039] C m H 2m +H2==C m H 2m+2

[0040] HCN+3H2==NH3+CH4

[0041] C4H4S+4H2==C4H 10 +H2S

[0042] RSH+H2==H2S+RH

[0043] RSR+2H2==H2S+2RH

[0044] RSSR+3H2==2H2S+2RH

[0045] CS2+4H2==2H2S+CH4

[0046] COS+H2==H2S+CO

[0047] COS+H2O==H2S+CO2

[0048] Conventional cobalt-molybdenum catalysts used in natural gas chemical processing, supported by activated alumina, produce large quantities of multi-carbon macromolecules during high-temperature hydrogenation, compromising the safe operation of subsequent processes. Furthermore, conventional molybdenum catalysts used in the petrochemical industry for oil hydrogenation often incorporate acidic additives such as phosphorus or fluorine to increase the support acidity and enhance hydrogenation activity. However, these acidic supports cannot be used with ammonia-containing gas sources, as they rapidly lose activity. Furthermore, while enhancing hydrogenation activity, these acidic supports can also lead to carbon deposition from CO disproportionation and methanation of CO and CO₂, causing catalyst overheating and deactivation. Conventional cobalt-molybdenum catalysts supported by activated alumina, when used in gas sources containing H₂O, CO, CO₂, and H₂, inevitably undergo a CO shift reaction or its reverse reaction, altering the effective composition of CO and H₂ in the gas. Furthermore, since the CO shift reaction is also highly exothermic, its occurrence also alters the catalyst bed temperature. This, combined with the intense heat release from the aforementioned side reactions, such as CO disproportionation and methanation, complicates reaction control and increases the risk of safety incidents.

[0049] The industrial gas purification catalyst used in this patent uses A-type molecular sieve to load active components, cleverly utilizes the 3-5 angstrom pore size distribution of A-type molecular sieve, and utilizes the characteristics of the molecular sieve pore structure to inhibit the generation of multi-carbon chain macromolecules. At the same time, it cooperates with the use of the remaining sodium, potassium, calcium and other alkali metals or alkaline earth metals on the molecular sieve to inhibit and reduce the occurrence of CO disproportionation, CO reduction and methanation of CO and CO2 and other side reactions, effectively avoiding catalyst runaway temperature and carbon deposition deactivation. At the same time, the sodium, potassium, calcium and other alkali metals or alkaline earth metals on the molecular sieve inhibit the adsorption of ammonia and can be used in a gas source containing NH3 (0.001% to 0.5%). In addition, sodium, potassium, calcium and other alkali metals or alkaline earth metals are also good carbon removers, which accelerate the elimination of a small amount of carbon precipitation in the catalyst due to CO disproportionation and avoid carbon accumulation on the catalyst carrier.

[0050] The industrial gas purification catalyst of the present invention effectively avoids the CO shift reaction or its reverse reaction without changing the content of effective components such as CO and H2 in the gas source. It also purifies oxygen, olefins, HCN, and complex sulfides such as thiophene, disulfide, mercaptan, sulfide, and CS2 at 230-450°C, and COS at 80-200°C.

[0051] The main effects of this patent are:

[0052] (1) The industrial gas purification catalyst provided by the present invention is suitable for removing and purifying ammonia and high CO+CO2 gas sources from industrial gases such as crude coal gas, blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, calcium carbide tail gas and other industrial waste gases. Its 3-5 angstrom pore size structure can inhibit the formation of multi-carbon chain macromolecules. At the same time, the residual sodium, potassium, calcium and other alkali metals or alkaline earth metals on the molecular sieve can inhibit and reduce the occurrence of side reactions such as CO disproportionation, CO reduction and methanation of CO and CO2, effectively avoiding catalyst runaway and carbon deposition deactivation. At the same time, the sodium, potassium, calcium and other alkali metals or alkaline earth metals on the molecular sieve inhibit the adsorption of ammonia and can be used in gas sources containing 0.001% to 0.5% NH3. In addition, sodium, potassium, calcium and other alkali metals or alkaline earth metals are also good carbon removers, accelerating the elimination of small amounts of carbon precipitated in the catalyst due to CO disproportionation and avoiding carbon accumulation on the catalyst carrier. At the same time, the CO shift reaction or its reverse reaction is effectively avoided without changing the content of effective components such as CO and H2 in the gas source.

[0053] (2) The industrial gas purification catalyst provided by the present invention has the function of purifying oxygen, olefins, HCN, and complex sulfides such as thiophene, disulfide, mercaptan, sulfide, and CS2 at 230-450°C, and COS at 80-200°C. It is used for the purification of oxygen, olefins, HCN, and complex sulfides such as thiophene, disulfide, mercaptan, sulfide, and CS2, as well as COS. The removal rates of oxygen, olefins, mercaptan, sulfide, disulfide, and CS2 are greater than 95%, and the removal rates of HCN, COS, and thiophene are greater than 90%. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 Schematic diagram of the reaction process of the present invention. DETAILED DESCRIPTION

[0055] The following examples further illustrate the content of the present invention.

[0056] Example 1:

[0057] (1) Take 100 g of 3A molecular sieve and pour it into 1 L of prepared 2 mol / L ammonium chloride solution, place it in a 3 L container, stir and heat to increase the temperature, exchange at 90 ° C for 3 hours, filter, wash, and dry at 120 ° C. Repeat the exchange three times, filter, wash, dry, and roast at 300 ° C for 3 hours for use.

[0058] (2) Prepare 1 L of 0.2 mol / L nickel nitrate (nickel nitrate hexahydrate) solution, add the powder obtained in (1), place it in a 3-liter container, stir and heat to 90°C, continue stirring for 5 hours, filter, wash, and dry at 120°C. Repeat the exchange three times, then filter, wash, and dry at 120°C for use.

[0059] (3) Take 8 g of ammonium molybdate (ammonium heptamolybdate tetrahydrate) to prepare a solution, add a small amount of ammonia water to dissolve it, and impregnate an equal amount of it on the powder obtained in (2), and dry it at 120°C for later use.

[0060] (4) After adding a binder to the material, it was extruded into strips with a diameter of 3 mm and activated at 500° C. for 3 hours to obtain the finished product A1 (which contained 6.3% MoO 3 and 3.3% NiO active components, and 73% alkali metal remained on the 3A molecular sieve without exchange).

[0061] Example 2:

[0062] (1) Take 100 g of 4A molecular sieve and pour it into 1 L of prepared 1 mol / L ammonium sulfate solution, place it in a 3 L container, stir and heat to increase the temperature, exchange at 90 ° C for 6 hours, filter, wash, and dry at 120 ° C. Repeat the exchange three times, filter, wash, dry, and roast at 350 ° C for 3 hours for use.

[0063] (2) Prepare 1 L of 0.3 mol / L cobalt nitrate (cobalt nitrate hexahydrate) solution, add the powder obtained in (1), place in a 3 L container, stir and heat to 90 ° C, continue stirring for 7 hours, filter, wash, and dry at 120 ° C. Repeat the exchange three times, filter, wash, and dry at 120 ° C for use.

[0064] (3) Take 10 g of ammonium molybdate (ammonium heptamolybdate tetrahydrate) to prepare a solution, add a small amount of ammonia water to dissolve it, and impregnate an equal amount of the solution onto the powder obtained in (2), and dry it at 120°C for later use.

[0065] (4) After adding a binder to the material, it was extruded into strips with a diameter of 5 mm and activated at 500° C. for 3 hours to obtain the finished product A2 (which contained 7.8% MoO 3 and 5.2% CoO active components, and 65% of the alkali metal remained unexchanged on the 4A molecular sieve).

[0066] Example 3:

[0067] (1) Take 100 g of 5A molecular sieve and pour it into 1 L of prepared 2 mol / L ammonium nitrate solution, place it in a 3 L container, stir and heat to increase the temperature, exchange at 90 ° C for 5 hours, filter, wash, and dry at 120 ° C. Repeat the exchange three times, filter, wash, dry, and roast at 400 ° C for 3 hours for use.

[0068] (2) Prepare 1 L of 0.4 mol / L nickel nitrate (nickel nitrate hexahydrate) solution, add the powder obtained in (1), place it in a 3-liter container, stir and heat to 90°C, continue stirring for 8 hours, filter, wash, and dry at 120°C. Repeat the exchange three times, then filter, wash, and dry at 120°C for use.

[0069] (3) Take 7.5g of ammonium metatungstate ((NH4)6W 12 O 39·2H2O) to prepare a solution, add a small amount of ammonia water to help dissolve it, and impregnate an equal amount of it onto the powder obtained in (2), and dry it at 120℃ for later use.

[0070] (4) After adding a binder to the material, it was extruded into strips with a diameter of 4 mm and activated at 550° C. for 3 hours to obtain the finished product A3 (which contained 6.9% WO 3 and 6.4% NiO active components, and 59% of the alkali metals and alkaline earth metals remaining on the 5A molecular sieve were not exchanged).

[0071] Example 4:

[0072] (1) Pour 100 g of 3A molecular sieve into 1 L of prepared 2 mol / L ammonium nitrate solution in a 3 L container, stir and heat to raise the temperature, exchange at 90 ° C for 9 hours, filter, wash, and dry at 120 ° C. Repeat the exchange three times, filter, wash, dry, and calcine at 300 ° C for 3 hours for use.

[0073] (2) Prepare 1 L of 0.3 mol / L cobalt nitrate (cobalt nitrate hexahydrate) solution, add the powder obtained in (1), place it in a 3-liter container, stir and heat to 90°C, continue stirring for 8 hours, filter, wash, and dry at 120°C. Repeat the exchange three times, then filter, wash, and dry at 120°C for use.

[0074] (3) Take 5g of ammonium metatungstate ((NH4)6W 12 O 39 ·2H2O) to prepare a solution, add a small amount of ammonia water to help dissolve it, and impregnate an equal amount of it onto the powder obtained in (2), and dry it at 120℃ for later use.

[0075] (4) After adding a binder, the material was extruded into strips with a diameter of 3 mm and activated at 450° C. for 6 hours to obtain the finished product A4 (containing 4.5% WO 3 and 5.1% CoO active components, and 63% alkali metal remaining on the 3A molecular sieve was not exchanged).

[0076] The catalyst samples prepared in Examples 1-4 above were subjected to a sulfurization treatment. The sulfurization treatment may specifically adopt the following sulfurization gas source and sulfurization steps:

[0077] The sulfide gas (in terms of volume fraction) consists of hydrogen sulfide (1%), hydrogen (10%), and the remainder is nitrogen.

[0078] Nitrogen was introduced into the reactor loaded with the catalyst sample, and the temperature was increased to sulfidation according to the conditions in Table 1. When the reactor temperature reached 200°C, the sulfidation process was switched to sulfide gas. At 400°C, the H2S volume fraction at the reactor inlet and outlet was analyzed until equilibrium was reached between the inlet and outlet H2S, indicating the end of the sulfidation process.

[0079] Table 1 Temperature-elevated vulcanization conditions

[0080]

[0081] The sulfided catalyst samples are used for the treatment of typical industrial gases such as crude coal gas, blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, calcium carbide tail gas, etc.

[0082] (1) The volume composition is 14% CO, 33% CO2, 39% H2, 12% CH4, 1% H2O, 0.4% C2H6, 0.2% O2, 0.1% C2H4, 0.2% H2S, 150ppm HCN, 150ppm COS, 300ppm NH3, 250ppm RSH (including various types of mercaptans), 11ppm dimethyl disulfide, 10ppm RSR (including methyl sulfide and ethyl sulfide), 8ppm CS2, 11ppm thiophene. The crude gas after separation by cooling at 40℃ in a typical Lurgi furnace is 30000Nm 3 / h, pressure 3.8MPa, when initially started, the temperature is raised to 350℃ by the heater, and the 10m 3 The 1# reactor bed of the industrial gas purification catalyst described in this patent can adjust the temperature of the reactor to 350°C by adjusting the gas volume through the heat exchanger and / or heating with a heater during the reaction process. The outlet gas of the 1# reactor exchanges heat with the inlet cold gas and passes through a gas cooler to reduce the temperature to 150°C before entering the 15m 3 The 2# reactor bed of the industrial gas purification catalyst described in this patent has its outlet gas enter the next stage, such as Figure 1 shown.

[0083] The four samples prepared above were evaluated in a typical Lurgi furnace crude gas having a volume composition of 14% CO, 33% CO2, 39% H2, 12% CH4, 1% H2O, 0.4% C2H6, 0.2% O2, 0.1% C2H4, 0.2% H2S, 150 ppm HCN, 150 ppm COS, 300 ppm NH3, 250 ppm RSH (containing various types of mercaptans), 11 ppm dimethyl ether, 10 ppm RSR (containing methyl sulfide and ethyl sulfide), 8 ppm CS2, and 11 ppm thiophene. The results are shown in Table 2:

[0084] Table 2

[0085]

[0086] At the same time, the composition of the outlet gas source was detected. The contents of CO, CO2, H2, and H2O did not change, indicating that no CO shift reaction and its reverse reaction occurred, and no C3 and above hydrocarbon substances C m H n (m≥3) is generated, and the CH4 increase is <0.1%.

[0087] (2) The volume composition is 8% CO, 3% CO2, 53% H2, 27% CH4, 6.5% N2, 1.5% H2O, 0.3% C2H6, 0.4% O2, 0.1% C2H4, 0.1% H2S, 500ppm HCN, 100ppm COS, 400ppm NH3, 120ppm RSH (including various types of mercaptans), 11ppm dimethyl disulfide, 8ppm RSR (including methyl sulfide and ethyl sulfide), 9ppm CS2, 5ppm thiophene. Typical coke oven gas 100000Nm 3 / h, pressure 2.5MPa, at the initial start-up, after heat exchange with the outlet gas of No. 1 reactor and heating to 320℃ through heater as needed, it first enters the 40m 3 The 1# reactor bed of the industrial gas purification catalyst described in this patent exchanges heat between the reactor outlet gas and the inlet cold gas. During the reaction operation, the reactor temperature can be adjusted to 320°C by adjusting the gas volume through the heat exchanger and / or heating with a heater. After the heat exchange between the reactor outlet gas and the inlet cold gas, the temperature is reduced to 120°C through a gas cooler and enters a 40m 3 The 2# reactor bed of the industrial gas purification catalyst described in this patent has its outlet gas enter the next stage, such as Figure 1 shown.

[0088] The four samples prepared above were evaluated in a typical coke oven gas having a volume composition of 8% CO, 3% CO2, 53% H2, 27% CH4, 6.5% N2, 1.5% H2O, 0.3% C2H6, 0.4% O2, 0.1% C2H4, 0.1% H2S, 500ppm HCN, 100ppm COS, 400ppm NH3, 120ppm RSH (containing various types of mercaptans), 11ppm dimethyl sulfide, 8ppm RSR (containing methyl sulfide and ethyl sulfide), 9ppm CS2, and 5ppm thiophene. The results are shown in Table 3:

[0089] Table 3

[0090]

[0091] At the same time, the composition of the outlet gas source was detected, and the contents of CO, CO2, H2, and H2O did not change, indicating that no CO shift reaction and its reverse reaction occurred, no C3 and above hydrocarbons were generated, and the CH4 increase was <0.1%.

[0092] (3) The volume composition is 74% CO, 6% CO2, 10% H2, 0.5% CH4, 6.5% N2, 2% H2O, 0.4% C2H6, 0.3% O2, 0.1% C2H4, 0.05% H2S, 300ppm HCN, 150ppm COS, 400ppm NH3, 45ppm RSH (including various types of mercaptans), 7ppm dimethyl disulfide, 5ppm RSR (including methyl sulfide and ethyl sulfide), 21ppm CS2. Typical calcium carbide gas 50000Nm 3 / h, pressure 2.8MPa, when initially started, the temperature is raised to 370℃ by the heater, and the 10m 3 The 1# reactor bed of the industrial gas purification catalyst described in this patent can heat exchange the reactor outlet gas and the inlet cold gas during the reaction operation, adjust the gas volume through the heat exchanger and / or adjust the reactor temperature to 370°C by heating with a heater, and the reactor outlet gas and the inlet cold gas are heat exchanged and the temperature is reduced to 200°C by a gas cooler before entering a 50m 3 The 2# reactor bed of the industrial gas purification catalyst described in this patent has its outlet gas enter the next stage, such as Figure 1 shown.

[0093] The four samples prepared above were evaluated in a typical carbide gas having a volume composition of 74% CO, 6% CO2, 10% H2, 0.5% CH4, 6.5% N2, 2% H2O, 0.4% C2H6, 0.3% O2, 0.1% C2H4, 0.05% H2S, 300ppm HCN, 150ppm COS, 400ppm NH3, 45ppm RSH (containing various types of mercaptans), 7ppm dimethyl ether, 5ppm RSR (containing methyl sulfide and ethyl sulfide), and 21ppm CS2. The results are shown in Table 4:

[0094] Table 4

[0095]

[0096] At the same time, the composition of the outlet gas source was detected, and the contents of CO, CO2, H2, and H2O did not change, indicating that no CO shift reaction and its reverse reaction occurred, no C3 and above hydrocarbons were generated, and the CH4 increase was <0.1%.

Claims

1. An industrial gas purification catalyst, characterized in that: The invention comprises a type A molecular sieve and MoO3 / WO3 and NiO / CoO loaded on the type A molecular sieve, wherein the content of molybdenum or tungsten is 3-12wt% in terms of MoO3 or WO3, and the content of nickel or cobalt is 3-7wt% in terms of NiO or CoO. The molecular sieve also contains 55%-75% of alkali metal or alkaline earth metal which has not been ion-exchanged in terms of molar ratio, wherein the alkali metal or alkaline earth metal is sodium, potassium or calcium.

2. The industrial gas purification catalyst according to claim 1, characterized in that: The pore size of type A molecular sieve is 3. The industrial gas purification catalyst according to claim 1, characterized in that: The type A molecular sieve is 3A, 4A or 5A molecular sieve.

4. The method for preparing the industrial gas purification catalyst according to claim 1, characterized in that: The specific steps include: (1) ion exchange the type A molecular sieve with an ammonium salt solution at 80-100°C for 3-10 hours, repeat the exchange multiple times, filter, wash, and then calcine at 300-400°C for use; (2) preparing a solution containing Ni / Co, stirring the solution with the powder obtained in step (1) at 80-100° C. for 5-8 hours, repeating the exchange multiple times, filtering, washing, and drying for later use; (3) preparing a solution containing the active component Mo / W, impregnating an equal amount of the solution onto the powder obtained in step (2), and drying the solution for later use; (4) Adding a binder to the powder obtained in step (3) and molding the powder, and activating the powder at 400-600° C. to complete the catalyst preparation.

5. The method for preparing an industrial gas purification catalyst according to claim 4, wherein: After the ion exchange in steps (1) and (2), the molecular sieve still contains alkali metal or alkaline earth metal sodium, potassium and calcium which have not been exchanged by ions in a molar ratio of 55% to 75%.

6. The method for preparing an industrial gas purification catalyst according to claim 4, wherein: The ammonium salt is selected from ammonium chloride, ammonium sulfate, and ammonium nitrate; the active components in the solution containing the active components Mo / W and Ni / Co are all salts thereof, selected from ammonium molybdate, ammonium metatungstate, nickel nitrate, and cobalt nitrate.

7. The method for preparing an industrial gas purification catalyst according to claim 4, wherein: According to the needs, ammonia water is used as a co-solvent in the solution of the active component Mo / W to prepare a solution of the active component salt; The shaped dosage form is spherical, bar or columnar.

8. Use of the industrial gas purification catalyst according to claim 1 in the catalytic purification of oxygen, olefins, HCN, complex sulfides and / or COS in ammonia-containing and high-CO+CO2 gas sources.

9. The use according to claim 8, characterized in that: The removal temperature of oxygen, olefins, HCN and complex sulfides is 230-450℃, and the removal temperature of COS is 80-200℃.

10. The use according to claim 8, wherein the ammonia- and high-CO+CO2-containing gas source is one or more of crude coal gas, blast furnace gas, converter gas, coke oven gas, yellow phosphorus tail gas, and calcium carbide tail gas, and the NH3 content is 0.001% to 0.5%, and the CO+CO2 content is greater than 10%.

Images