CN116371392A - Integrated desulfurization and decyanation catalyst and preparation method and application thereof - Google Patents

Integrated desulfurization and decyanation catalyst and preparation method and application thereof Download PDF

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CN116371392A
CN116371392A CN202310208608.2A CN202310208608A CN116371392A CN 116371392 A CN116371392 A CN 116371392A CN 202310208608 A CN202310208608 A CN 202310208608A CN 116371392 A CN116371392 A CN 116371392A
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hours
decyanation
integrated desulfurization
carbon powder
catalyst
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朱廷钰
李玉然
林玉婷
刘旭东
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Institute of Process Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/006—Hydrogen cyanide

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Abstract

The invention provides an integrated desulfurization and decyanation catalyst, and a preparation method and application thereof. The integrated desulfurization and decyanation catalyst provided by the invention simultaneously realizes COS and H 2 S and HCN are removed, and H is removed 2 The influence on the removal efficiency of COS and HCN is reduced during S, so that the service life is longer, and the integrated desulfurization and decyanation catalyst is usedThe floor area of the blast furnace gas desulfurization and decyanation device can be reduced.

Description

Integrated desulfurization and decyanation catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and relates to an integrated desulfurization and decyanation catalyst, in particular to an integrated desulfurization and decyanation catalyst and a preparation method and application thereof.
Background
The blast furnace gas comprises 25-30% CO and 9-12% CO 2 7 to 10 percent of H 2 O, 1-4% H 2 Small amounts of hydrocarbons and sulfur-containing components. Wherein the total amount of sulfur-containing components is about 200 to 300mg/m 3 Wherein more than 90% is carbonyl sulfide (COS) of about 180-300 mg/m 3 ，H 2 S is about 5-50 mg/m 3 The remainder is carbon disulphide (CS 2 ) And other organosulfur, about 5mg/m 3 . Moreover, the concentration of HCN in blast furnace gas is higher than that of sulfur, and is generally 150-700 mg/m 3 。
The development of the purification technology of the carbon emission source with the largest proportion in the blast furnace gas and the steel industry enters the acceleration period, and the CO 2 Adsorption/absorption agent pair COS, H 2 S, HCN is very sensitive to the presence of, and therefore CO is currently in common use 2 The trapping method, such as pressure swing adsorption and chemical absorption, requires a front desulfurizing and decyanating device. One of the difficulties in the industrialization of blast furnace gas cleaning technology is that the blast furnace area is often arranged too compactly and the space of the carbon capture related device is also required to be reserved, so that higher requirements are put on the occupation area of the pre-treated blast furnace gas desulfurization and decyanation device. However, it is difficult to realize desulfurization and decyanation simultaneously by using the catalyst in the currently disclosed desulfurization and decyanation device for blast furnace gas, and if desulfurization and decyanation are realized by using a plurality of catalysts, the occupation area of the desulfurization and decyanation device for blast furnace gas is increased.
CN115106108A discloses a COS hydrolysis catalyst for blast furnace gas and a preparation method thereof, wherein the COS hydrolysis catalyst for blast furnace gas comprises a carrier, an active component and an additive carried on the carrier; the chemical components of the carrier comprise alumina, titanium oxide, silicon dioxide and magnesium oxide; the chemical components of the active component comprise potassium carbonate and sodium carbonate; the chemical components of the additive comprise nickel carbonate, cobalt carbonate, ammonium molybdate and potassium manganate. The COS hydrolysis catalyst for blast furnace gas is prepared by loading active components and additives on a carrier through an impregnation method. The COS hydrolysis catalyst for blast furnace gas has the advantages of sulfur resistance, oxygen resistance, sulfation resistance, HCN resistance and other acid gas corrosion resistance The low-temperature activity is excellent, and the like, and the low-temperature catalyst is not only strong in low-temperature toxicity resistance, high in COS hydrolysis conversion rate and slow in activity reduction, but also suitable for large-scale devices such as blast furnace gas and the like. However, although the COS hydrolysis catalyst for blast furnace gas can realize sulfur and oxygen resistance, the catalyst can not simultaneously realize the removal of HCN, is only used for the hydrolysis of COS, and also needs to arrange H after the hydrolysis 2 S removing device.
CN112058273a discloses a blast furnace gas desulfurization catalyst, a preparation method and application thereof. The desulfurization catalyst comprises an active carbon carrier, an active component and a promoter, wherein the active component is one or a combination of more of zinc oxide, ferric oxide, manganese oxide and copper oxide, and the promoter is alkali metal or alkaline earth metal oxide. The preparation method comprises the following steps: (1) Carrying out functional group and surface acid-base modification treatment on the active carbon carrier; (2) Preparing an active component solution, loading an active component on a modified active carbon carrier by adopting an impregnation method, drying and roasting; (3) Preparing a cocatalyst component solution, loading the cocatalyst component on the modified active carbon carrier by adopting an impregnation method, drying and roasting to prepare the desulfurization catalyst. The catalyst is used for removing sulfide in blast furnace gas, and reducing the concentration of sulfide to 20mg/Nm 3 In addition, the saturated sulfur capacity is more than 20%, and the catalyst still has higher activity after multiple regenerations, so that the gas desulfurization cost can be greatly reduced. Also, the blast furnace gas desulfurization catalyst cannot simultaneously realize the removal of HCN.
The prior art has certain defects in the blast furnace gas catalysts, and COS and H cannot be realized at the same time 2 And S and HCN are removed. Therefore, development and design of a novel integrated desulfurization and decyanation catalyst and a preparation method thereof are important.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an integrated desulfurization and decyanation catalyst and a preparation method and application thereof, and the integrated desulfurization and decyanation catalyst provided by the invention realizes COS and H simultaneously 2 S and HCN are removed, and H is removed 2 The influence on the removal efficiency of COS and HCN is reduced during S, so that the service life is longer, and the integrated device is usedThe catalyst can also reduce the floor area of the blast furnace gas desulfurization and decyanation device.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an integrated desulfurization and decyanation catalyst comprising an alkali modified activated carbon and a desulfurizing agent supported on the alkali modified activated carbon.
The integrated desulfurization and decyanation catalyst provided by the invention comprises alkali modified activated carbon, and the surface of the alkali modified activated carbon has certain alkalinity, so that COS and H in blast furnace gas are promoted 2 The adsorption efficiency of S and HCN can also catalyze the hydrolysis reaction of COS and HCN to realize the removal of COS and HCN, wherein the integrated desulfurization and decyanation catalyst plays the roles of an adsorbent and a catalyst; meanwhile, the desulfurizing agent loaded on the surface of the alkali modified activated carbon can improve H 2 S to sulfate conversion efficiency, thereby realizing H generated by COS hydrolysis reaction 2 S and H in furnace gas 2 S, removing; the integrated desulfurization and decyanation catalyst can realize COS and H simultaneously 2 S and HCN are removed.
Since the removal of COS and HCN by hydrolysis reaction is realized by the catalysis of alkali modified activated carbon, H 2 S is removed by catalysis of a desulfurizing agent loaded on the surface of the alkali modified active carbon, so that the integrated desulfurizing and decyanating catalyst hydrolyzes and removes active sites of COS and HCN and removes H 2 S active sites are separated, and H is removed by an integrated desulfurization and decyanation catalyst 2 And S has reduced influence on the hydrolysis efficiency of COS and HCN, so that the service life of the integrated desulfurization and decyanation catalyst is prolonged.
The integrated desulfurization and decyanation catalyst provided by the invention is used for a pretreated blast furnace gas desulfurization and decyanation device, so that desulfurization and decyanation are performed in the same tower, the occupied area of the blast furnace gas desulfurization and decyanation device is reduced, and the possibility of popularizing the integrated desulfurization and decyanation catalyst in the established blast furnace is promoted.
The integrated desulfurization and decyanation catalyst provided by the invention simultaneously realizes COS and H 2 S and HCN are removed, and H is removed 2 The influence on the removal efficiency of COS and HCN is reduced during S, so that the service life is longer, and the floor area of the blast furnace gas desulfurization and decyanation device can be reduced by using the integrated desulfurization and decyanation catalyst.
Preferably, the surface of the alkali modified activated carbon has pyridine and/or pyrrole.
Preferably, the alkali modified activated carbon is any one or a combination of at least two of potassium hydroxide modified activated carbon, sodium hydroxide modified activated carbon or calcium hydroxide modified activated carbon, and typical but non-limiting combinations include a combination of potassium hydroxide modified activated carbon and sodium hydroxide modified activated carbon, a combination of sodium hydroxide modified activated carbon and calcium hydroxide modified activated carbon, a combination of potassium hydroxide modified activated carbon and calcium hydroxide modified activated carbon, or a combination of potassium hydroxide modified activated carbon, sodium hydroxide modified activated carbon and calcium hydroxide modified activated carbon, preferably potassium hydroxide modified activated carbon.
Preferably, the desulfurizing agent comprises any one or a combination of at least two of a calcium-based desulfurizing agent, a sodium-based desulfurizing agent, an amino-based desulfurizing agent, a magnesium-based desulfurizing agent, or an iron-based desulfurizing agent, and typical but non-limiting combinations include combinations of a calcium-based desulfurizing agent and a sodium-based desulfurizing agent, combinations of a sodium-based desulfurizing agent and an amino-based desulfurizing agent, combinations of an amino-based desulfurizing agent and a magnesium-based desulfurizing agent, combinations of a magnesium-based desulfurizing agent and an iron-based desulfurizing agent, combinations of a calcium-based desulfurizing agent, a sodium-based desulfurizing agent and an amino-based desulfurizing agent, or combinations of a sodium-based desulfurizing agent, an amino-based desulfurizing agent, a magnesium-based desulfurizing agent and an iron-based desulfurizing agent.
Preferably, the desulfurizing agent is ferric oxide.
In the invention, the mass percent of the integrated desulfurization and decyanation catalyst is 77 to 78.5 percent, the mass percent of the potassium element is 4.2 to 4.6 percent, the mass percent of the iron element is 1.8 to 2.3 percent, the mass percent of the sulfur element is 0.1 to 0.4 percent, the mass percent of the hydrogen element is 0.05 to 0.15 percent, the mass percent of the oxygen element is 13.4 to 13.8 percent, and the mass percent of the impurity element is 0.25 to 3.45 percent.
The mass fraction of the carbon element in the integrated desulfurization and decyanation catalyst in the present invention is 77 to 78.5wt%, for example, 77wt%, 77.1wt%, 77.2wt%, 77.3wt%, 77.4wt%, 77.5wt%, 77.6wt%, 77.7wt%, 77.8wt%, 77.9wt%, 78wt%, 78.1wt%, 78.2wt%, 78.3wt%, 78.4wt% or 78.5wt%, but the catalyst is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The mass fraction of potassium element in the integrated desulfurization and decyanation catalyst of the present invention is 4.2 to 4.6wt%, for example, 4.2wt%, 4.25wt%, 4.3wt%, 4.35wt%, 4.4wt%, 4.45wt%, 4.5wt%, 4.55wt% or 4.6wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The mass fraction of the iron element in the integrated desulfurization and decyanation catalyst in the present invention is 1.8 to 2.3wt%, for example, 1.8wt%, 1.85wt%, 1.9wt%, 1.95wt%, 2wt%, 2.05wt%, 2.1wt%, 2.15wt%, 2.2wt%, 2.25wt% or 2.3wt%, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The mass fraction of the sulfur element in the integrated desulfurization and decyanation catalyst in the present invention is 0.1 to 0.4wt%, for example, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt% or 0.4wt%, but the catalyst is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The mass fraction of the hydrogen element in the integrated desulfurization and decyanation catalyst in the present invention is 0.05 to 0.15wt%, for example, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, 0.1wt%, 0.11wt%, 0.12wt%, 0.13wt%, 0.14wt% or 0.15wt%, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The mass fraction of oxygen in the integrated desulfurization and decyanation catalyst of the present invention is 13.4 to 13.8wt%, for example, 13.4wt%, 13.45wt%, 13.5wt%, 13.55wt%, 13.6wt%, 13.65wt%, 13.7wt%, 13.75wt% or 13.8wt%, but the present invention is not limited to the recited values, and other non-recited values in the range of the recited values are equally applicable.
The mass fraction of the impurity element in the integrated desulfurization and decyanation catalyst of the present invention is 0.25 to 3.45wt%, for example, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, 0.5wt%, 0.55wt%, 0.6wt%, 0.65wt%, 0.7wt%, 0.75wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.6wt%, 2.8wt%, 3wt%, 3.2wt%, 3.4wt% or 3.45wt%, but the present invention is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical.
Preferably, the height of the cylinder is 10-14 mm, and the diameter of the bottom surface is 8-10 mm.
The height of the cylinder in the present invention is 10 to 14mm, and for example, it may be 10mm, 10.2mm, 10.4mm, 10.6mm, 10.8mm, 11mm, 11.2mm, 11.4mm, 11.6mm, 11.8mm, 12mm, 12.2mm, 12.4mm, 12.6mm, 12.8mm, 13mm, 13.2mm, 13.4mm, 13.6mm, 13.8mm or 14mm, but not limited to the above values, and other values not listed in the above numerical range are equally applicable.
The diameter of the cylindrical bottom surface in the present invention is 8 to 10mm, and for example, 8mm, 8.2mm, 8.4mm, 8.6mm, 8.8mm, 9mm, 9.2mm, 9.4mm, 9.6mm, 9.8mm or 10mm may be used, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical range are applicable.
In a second aspect, the present invention provides a method for preparing the integrated desulfurization and decyanation catalyst in the first aspect, which comprises:
and (3) mixing the carbon powder with alkali to obtain alkali modified carbon powder, and activating the alkali modified carbon powder and the desulfurizing agent after mixing the alkali modified carbon powder and the desulfurizing agent to obtain the integrated desulfurization and decyanation catalyst.
Preferably, the mass ratio of carbon powder to alkali in the first mixture is 100 (8-12), for example, may be 100:8, 100:8.5, 100:9, 100:10, 100:10.5, 100:11, 100:11.5 or 100:12, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the base comprises any one or a combination of at least two of potassium hydroxide, sodium hydroxide and calcium hydroxide, typically but not limited to, potassium hydroxide in combination with sodium hydroxide, sodium hydroxide in combination with calcium hydroxide, potassium hydroxide in combination with calcium hydroxide, or potassium hydroxide, sodium hydroxide in combination with calcium hydroxide, preferably potassium hydroxide.
Preferably, the first mixing mode comprises first stirring, wherein the rotating speed of the first stirring is 50-60 r/s, the time is 3-5 h, and the temperature is 20-30 ℃;
The rotation speed of the first stirring in the present invention is 50 to 60r/s, and may be, for example, 50r/s, 51r/s, 52r/s, 53r/s, 54r/s, 55r/s, 56r/s, 57r/s, 58r/s, 59r/s or 60r/s, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The first stirring time in the present invention is 3 to 5 hours, and may be, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5 hours, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The temperature of the first stirring in the present invention may be 20 to 30℃and may be, for example, 20℃and 21℃and 22℃and 23℃and 24℃and 25℃and 26℃and 27℃and 28℃and 29℃or 30℃and is not limited to the values listed, but other values not listed in the range are equally applicable.
Preferably, the first mixing and the second mixing further comprise a first standing and a first cleaning which are sequentially performed.
Preferably, the first standing time is 3 to 5 hours, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5 hours, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the first washing includes washing to a pH of 6.8-7.6, which may be, for example, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5 or 7.6, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the mass ratio of the alkali modified carbon powder to the desulfurizing agent in the second mixture is 100 (5-9), for example, it may be 100:5, 100:5.5, 100:6, 100:6.5, 100:7, 100:7.5, 100:8, 100:8.5 or 100:9, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the second mixing mode comprises second stirring, wherein the rotation speed of the second stirring is 50-60 r/s, the time is 3-5 h, and the temperature is 20-30 ℃.
The rotation speed of the second stirring in the present invention is 50 to 60r/s, and may be, for example, 50r/s, 51r/s, 52r/s, 53r/s, 54r/s, 55r/s, 56r/s, 57r/s, 58r/s, 59r/s or 60r/s, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The second stirring time in the present invention is 3 to 5 hours, and may be, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5 hours, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The temperature of the second stirring in the present invention may be 20 to 30℃and may be, for example, 20℃and 21℃and 22℃and 23℃and 24℃and 25℃and 26℃and 27℃and 28℃and 29℃or 30℃and is not limited to the values listed, but other values not listed in the range are equally applicable.
Preferably, the second mixing and the activating further comprise a second standing and a second cleaning which are sequentially carried out;
preferably, the second standing time is 3 to 5 hours, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5 hours, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the second washing includes washing to a pH of 6.8-7.6, which may be, for example, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5 or 7.6, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the activation comprises a heat treatment in steam.
Preferably, the heat treatment includes sequentially heating and insulating.
Preferably, the heating rate is 70-80 ℃/h, and the end temperature is 800-1000 ℃.
The rate of temperature rise in the present invention is 70 to 80℃per hour, and may be, for example, 70℃per hour, 71℃per hour, 72℃per hour, 73℃per hour, 74℃per hour, 75℃per hour, 76℃per hour, 77℃per hour, 78℃per hour, 79℃per hour or 80℃per hour, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
The end temperature of the temperature rise in the present invention may be 800 to 1000 ℃, for example, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, or 1000 ℃, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are similarly applicable.
Preferably, the time for the heat preservation is 40 to 56h, for example, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h, 48h, 49h, 50h, 51h, 52h, 53h, 54h, 55h or 56h, but not limited to the values listed, other non-listed values in the range are applicable, and the temperature for the heat preservation is the end temperature of the temperature rise.
Preferably, the preparation method of the carbon powder comprises the following steps:
and sieving, drying, dehydrating, carbonizing and ball milling anthracite to obtain the carbon powder.
The carbon content of the anthracite is more than 90 percent (dry basis), the volatile yield is less than 10 percent (dry ash basis), and the anthracite has no colloid layer thickness.
Preferably, the temperature of the drying and dehydration is 100-140 ℃ and the time is 10-14 h.
The drying and dehydrating temperature in the present invention may be, for example, 100℃to 140℃and 105℃to 110℃to 115℃to 120℃to 125℃to 130℃to 135℃or 140℃but is not limited to the values listed, and other values not listed in the range are applicable.
The drying and dehydrating time in the present invention is 10 to 14 hours, and may be, for example, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours or 14 hours, but is not limited to the listed values, and other non-listed values within the range of the values are equally applicable.
Preferably, the carbonization comprises a first carbonization heating, a second carbonization heating and carbonization heat preservation which are sequentially carried out in a protective atmosphere.
Preferably, the heating rate of the first carbonization heating is 20-40 ℃/min, and the end point temperature is 350-450 ℃.
The heating rate of the first carbonization heating in the present invention is 20 to 40 ℃/min, and may be, for example, 20 ℃/min, 22 ℃/min, 24 ℃/min, 26 ℃/min, 28 ℃/min, 30 ℃/min, 32 ℃/min, 34 ℃/min, 36 ℃/min, 38 ℃/min or 40 ℃/min, but the invention is not limited to the recited values, and other values not recited in the range of values are equally applicable.
In the present invention, the final temperature of the first carbonization temperature rise is 350 to 450 ℃, and for example, it may be 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, or 450 ℃, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are applicable.
Preferably, the temperature rising rate of the second carbonization temperature rising is 2-8 ℃/min, and the end point temperature is 500-600 ℃.
The heating rate of the second carbonization heating in the present invention is 2 to 8 ℃/min, and may be, for example, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.5 ℃/min or 8 ℃/min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
The final temperature of the second carbonization temperature rise in the present invention may be 500 to 600 ℃, for example, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, or 600 ℃, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are applicable.
Preferably, the carbonization heat-preserving time is 1.5 to 3 hours, for example, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3 hours, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the carbon powder having a size of 80 to 120 mesh obtained after the ball milling may be, for example, 80 mesh, 85 mesh, 90 mesh, 95 mesh, 100 mesh, 105 mesh, 110 mesh, 115 mesh or 120 mesh, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the preparation method further comprises granulation after the activation.
Preferably, the pelletization results in cylindrical integrated desulfurization and decyanation catalyst particles.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 100-140 ℃ for 10-14 h, carbonizing and ball milling to obtain the carbon powder with the size of 80-120 meshes, wherein the carbonizing comprises heating to 350-450 ℃ at the speed of 20-40 ℃/min in a protective atmosphere, heating to 500-600 ℃ at the speed of 2-8 ℃/min, and preserving heat for 1.5-3 h;
(2) Stirring and mixing carbon powder obtained in the step (1) with potassium hydroxide for 3-5 hours at the temperature of 20-30 ℃ at the rotating speed of 50-60 r/s for 100 (8-12) for 3-5 hours, standing for 3-5 hours, and cleaning until the pH value is 6.8-7.6 to obtain alkali modified carbon powder;
(3) And (3) at the temperature of 20-30 ℃, stirring and mixing the alkali modified carbon powder obtained in the step (2) with the mass ratio of 100 (5-9) for 3-5 hours at the rotating speed of 50-60 r/s, standing for 3-5 hours, cleaning to pH of 6.8-7.6, heating to 800-1000 ℃ in steam at the speed of 70-80 ℃/h, and preserving heat for 40-56 hours to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
In a third aspect, the present invention provides the use of an integrated desulfurization and decyanation catalyst according to the first aspect for integrated desulfurization and decyanation of blast furnace gas.
Compared with the prior art, the invention has the following beneficial effects:
the integrated desulfurization and decyanation catalyst provided by the invention simultaneously realizes COS and H 2 S and HCN are removed, and H is removed 2 The influence on the removal efficiency of COS and HCN is reduced during S, so that the service life is longer, and the floor area of the blast furnace gas desulfurization and decyanation device can be reduced by using the integrated desulfurization and decyanation catalyst.
Drawings
FIG. 1 is a graph showing the nitrogen 1s peak test of the X-ray photoelectron spectroscopy technique of the integrated desulfurization and decyanation catalyst in example 1.
FIG. 2 is a graph of the nitrogen 1s peak test of the X-ray photoelectron spectroscopy technique of the integrated desulfurization and decyanation catalyst in comparative example 3.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides an integrated desulfurization and decyanation catalyst, which comprises potassium hydroxide modified activated carbon and ferric oxide loaded on the potassium hydroxide modified activated carbon, wherein pyridine and pyrrole are arranged on the surface of the potassium hydroxide modified activated carbon;
The appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 12mm, and the diameter of the bottom surface is 9mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 120 ℃ for 12 hours, carbonizing and ball milling to obtain carbon powder with the size of 100 meshes, wherein the carbonizing comprises heating to 400 ℃ at the speed of 30 ℃/min in a protective atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, and then preserving heat for 2.4 hours;
(2) At the temperature of 25 ℃, the carbon powder and potassium hydroxide obtained in the step (1) with the stirring and mixing mass ratio of 100:10 are stirred and mixed for 4 hours at the rotating speed of 55r/s, and the mixture is stood for 4 hours and washed until the pH value is 7.2, so as to obtain alkali modified carbon powder;
(3) And (3) at the temperature of 25 ℃, stirring and mixing the alkali modified carbon powder and ferric oxide obtained in the step (2) with the mass ratio of 100:7 at the speed of 55r/s for 4 hours, standing for 4 hours, cleaning to pH of 7.2, heating to 900 ℃ in steam at the speed of 75 ℃/h, and preserving heat for 48 hours to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
Example 2
The embodiment provides an integrated desulfurization and decyanation catalyst, which comprises potassium hydroxide modified activated carbon and ferric oxide loaded on the potassium hydroxide modified activated carbon, wherein pyridine and pyrrole are arranged on the surface of the potassium hydroxide modified activated carbon;
The appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 11mm, and the diameter of the bottom surface is 9.5mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 110 ℃ for 13 hours, carbonizing and ball milling to obtain 80-mesh carbon powder, wherein the carbonizing comprises heating to 380 ℃ at a speed of 25 ℃/min in a protective atmosphere, heating to 580 ℃ at a speed of 6 ℃/min, and then preserving heat for 2 hours;
(2) At the temperature of 22 ℃, the carbon powder obtained in the step (1) and potassium hydroxide are stirred and mixed for 3.5 hours at the rotating speed of 58r/s and the mass ratio of 100:11, and are kept stand for 4.5 hours, and are cleaned to pH 7, so that alkali modified carbon powder is obtained;
(3) And (2) at the temperature of 22 ℃, stirring and mixing the alkali modified carbon powder and ferric oxide obtained in the step (2) with the mass ratio of 100:5 for 4.5h at the rotating speed of 52r/s, standing for 3.5h, cleaning to pH of 7, heating to 850 ℃ in steam at the speed of 72 ℃/h, and preserving heat for 52h to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
Example 3
The embodiment provides an integrated desulfurization and decyanation catalyst, which comprises potassium hydroxide modified activated carbon and ferric oxide loaded on the potassium hydroxide modified activated carbon, wherein pyridine and pyrrole are arranged on the surface of the potassium hydroxide modified activated carbon;
The appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 13mm, and the diameter of the bottom surface is 8.5mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 130 ℃ for 11 hours, carbonizing and ball milling to obtain carbon powder with the size of 90 meshes, wherein the carbonizing comprises heating to 350 ℃ at the speed of 35 ℃/min in a protective atmosphere, heating to 520 ℃ at the speed of 3 ℃/min, and then preserving heat for 2.7 hours;
(2) At 20 ℃, the carbon powder and potassium hydroxide obtained in the step (1) with the stirring and mixing mass ratio of 100:12 are stirred and mixed for 3 hours at the rotating speed of 60r/s, and are kept stand for 3.5 hours, and are cleaned to pH of 7.6, so that alkali modified carbon powder is obtained;
(3) And (3) at the temperature of 20 ℃, stirring and mixing the alkali modified carbon powder and ferric oxide obtained in the step (2) with the mass ratio of 100:6 at the rotating speed of 50r/s for 5 hours, standing for 4.5 hours, cleaning to pH of 7.6, heating to 950 ℃ in steam at the speed of 78 ℃/h, and preserving heat for 44 hours to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
Example 4
The embodiment provides an integrated desulfurization and decyanation catalyst, which comprises potassium hydroxide modified activated carbon and ferric oxide loaded on the potassium hydroxide modified activated carbon, wherein pyridine and pyrrole are arranged on the surface of the potassium hydroxide modified activated carbon;
The appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 10mm, and the diameter of the bottom surface is 8mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 100 ℃ for 14 hours, carbonizing and ball milling to obtain carbon powder with the size of 110 meshes, wherein the carbonizing comprises heating to 450 ℃ at the speed of 40 ℃/min in a protective atmosphere, heating to 500 ℃ at the speed of 2 ℃/min, and preserving heat for 3 hours;
(2) At the temperature of 28 ℃, the carbon powder obtained in the step (1) and potassium hydroxide are stirred and mixed for 4.5 hours at the rotating speed of 52r/s and the mass ratio of 100:8, and are kept stand for 3 hours, and are cleaned to the pH value of 6.8, so that alkali modified carbon powder is obtained;
(3) And (3) at the temperature of 28 ℃, stirring and mixing the alkali modified carbon powder and ferric oxide obtained in the step (2) with the mass ratio of 100:8 at the rotating speed of 60r/s for 3 hours, standing for 5 hours, cleaning to pH of 6.8, heating to 1000 ℃ in steam at the speed of 80 ℃/h, and preserving heat for 40 hours to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
Example 5
The embodiment provides an integrated desulfurization and decyanation catalyst, which comprises potassium hydroxide modified activated carbon and ferric oxide loaded on the potassium hydroxide modified activated carbon, wherein pyridine and pyrrole are arranged on the surface of the potassium hydroxide modified activated carbon;
The appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 14mm, and the diameter of the bottom surface is 10mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 140 ℃ for 10 hours, carbonizing and ball milling to obtain carbon powder with the size of 120 meshes, wherein the carbonizing comprises heating to 420 ℃ at the speed of 20 ℃/min in a protective atmosphere, heating to 600 ℃ at the speed of 8 ℃/min, and preserving heat for 1.5 hours;
(2) At the temperature of 30 ℃, the carbon powder and potassium hydroxide obtained in the step (1) with the stirring and mixing mass ratio of 100:9 are stirred and mixed for 5 hours at the rotating speed of 50r/s, and the mixture is stood for 5 hours and washed until the pH value is 7.4, so as to obtain alkali modified carbon powder;
(3) And (3) at the temperature of 30 ℃, mixing the alkali modified carbon powder and ferric oxide obtained in the step (2) with the stirring and mixing mass ratio of 100:9 at the rotating speed of 58r/s for 3.5h, standing for 3h, cleaning to pH of 7.4, heating to 800 ℃ in steam at the speed of 70 ℃/h, and preserving heat for 56h to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
Example 6
The embodiment provides an integrated desulfurization and decyanation catalyst, which comprises calcium hydroxide modified activated carbon and ferric oxide loaded on the calcium hydroxide modified activated carbon, wherein pyridine and pyrrole are arranged on the surface of the calcium hydroxide modified activated carbon;
The appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 12mm, and the diameter of the bottom surface is 9mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 120 ℃ for 12 hours, carbonizing and ball milling to obtain carbon powder with the size of 100 meshes, wherein the carbonizing comprises heating to 400 ℃ at the speed of 30 ℃/min in a protective atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, and then preserving heat for 2.4 hours;
(2) At the temperature of 25 ℃, the carbon powder and the calcium hydroxide obtained in the step (1) with the stirring and mixing mass ratio of 100:10 are stirred and mixed for 4 hours at the rotating speed of 55r/s, and the mixture is stood for 4 hours and washed until the pH value is 7.2, so that the alkali modified carbon powder is obtained;
(3) And (3) at the temperature of 25 ℃, stirring and mixing the alkali modified carbon powder and ferric oxide obtained in the step (2) with the mass ratio of 100:7 at the speed of 55r/s for 4 hours, standing for 4 hours, cleaning to pH of 7.2, heating to 900 ℃ in steam at the speed of 75 ℃/h, and preserving heat for 48 hours to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
Example 7
The embodiment provides an integrated desulfurization and decyanation catalyst, which comprises potassium hydroxide modified activated carbon and zinc oxide loaded on the potassium hydroxide modified activated carbon, wherein pyridine and pyrrole are arranged on the surface of the potassium hydroxide modified activated carbon;
The appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 12mm, and the diameter of the bottom surface is 9mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 120 ℃ for 12 hours, carbonizing and ball milling to obtain carbon powder with the size of 100 meshes, wherein the carbonizing comprises heating to 400 ℃ at the speed of 30 ℃/min in a protective atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, and then preserving heat for 2.4 hours;
(2) At the temperature of 25 ℃, the carbon powder and potassium hydroxide obtained in the step (1) with the stirring and mixing mass ratio of 100:10 are stirred and mixed for 4 hours at the rotating speed of 55r/s, and the mixture is stood for 4 hours and washed until the pH value is 7.2, so as to obtain alkali modified carbon powder;
(3) And (3) at the temperature of 25 ℃, the alkali modified carbon powder and zinc oxide obtained in the step (2) with the stirring and mixing mass ratio of 100:7 and the time of 4h are subjected to standing for 4h, the pH value is 7.2, the temperature is increased to 900 ℃ at the speed of 75 ℃/h in steam, the temperature is kept for 48h, the integrated desulfurization and decyanation catalyst is obtained, and the cylindrical integrated desulfurization and decyanation catalyst particles are obtained after granulation.
Example 8
The present example provided an integrated desulfurization and decyanation catalyst, the remainder being the same as example 1, except that the mass ratio of carbon powder to potassium hydroxide in step (2) of the preparation method of the integrated desulfurization and decyanation catalyst was 100:5.
Example 9
The present example provided an integrated desulfurization and decyanation catalyst, the remainder being the same as example 1, except that the mass ratio of carbon powder to potassium hydroxide in step (2) of the preparation method of the integrated desulfurization and decyanation catalyst was 100:15.
Example 10
The present example provided an integrated desulfurization and decyanation catalyst, the remainder being the same as example 1, except that the mass ratio of alkali-modified carbon powder to ferric oxide in step (3) of the preparation method of the integrated desulfurization and decyanation catalyst was 100:2.
Example 11
The present example provided an integrated desulfurization and decyanation catalyst, the remainder being the same as example 1, except that the mass ratio of alkali-modified carbon powder to ferric oxide in step (3) of the preparation method of the integrated desulfurization and decyanation catalyst was 100:12.
Comparative example 1
The comparative example provides an integrated desulfurization and decyanation catalyst comprising activated carbon and ferric oxide loaded on the activated carbon;
the appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 12mm, and the diameter of the bottom surface is 9mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 120 ℃ for 12 hours, carbonizing and ball milling to obtain carbon powder with the size of 100 meshes, wherein the carbonizing comprises heating to 400 ℃ at the speed of 30 ℃/min in a protective atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, and then preserving heat for 2.4 hours;
(2) And (3) at the temperature of 25 ℃, carrying out standing for 4 hours on the carbon powder and ferric oxide obtained in the step (1) with the stirring and mixing mass ratio of 100:7 and the rotating speed of 55r/s and the time of 4 hours, heating to 900 ℃ in steam at the speed of 75 ℃/h, and carrying out heat preservation for 48 hours to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
Comparative example 2
The comparative example provides an integrated desulfurization and decyanation catalyst, which comprises potassium hydroxide modified activated carbon, wherein pyridine and pyrrole are arranged on the surface of the potassium hydroxide modified activated carbon;
the appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 12mm, and the diameter of the bottom surface is 9mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 120 ℃ for 12 hours, carbonizing and ball milling to obtain carbon powder with the size of 100 meshes, wherein the carbonizing comprises heating to 400 ℃ at the speed of 30 ℃/min in a protective atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, and then preserving heat for 2.4 hours;
(2) At the temperature of 25 ℃, the carbon powder and potassium hydroxide obtained in the step (1) with the stirring and mixing mass ratio of 100:10 are stirred and mixed for 4 hours at the rotating speed of 55r/s, and the mixture is stood for 4 hours and washed until the pH value is 7.2, so as to obtain alkali modified carbon powder;
(3) And (3) heating the alkali modified carbon powder obtained in the step (2) to 900 ℃ in steam at a speed of 75 ℃/h, and preserving heat for 48h to obtain an integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
Comparative example 3
This comparative example provides an integrated desulfurization and decyanation catalyst comprising activated carbon;
the appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical, the height of the cylindrical shape is 12mm, and the diameter of the bottom surface is 9mm.
The preparation method of the integrated desulfurization and decyanation catalyst comprises the following steps:
(1) Sieving anthracite, drying and dehydrating at 120 ℃ for 12 hours, carbonizing and ball milling to obtain carbon powder with the size of 100 meshes, wherein the carbonizing comprises heating to 400 ℃ at the speed of 30 ℃/min in a protective atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, and then preserving heat for 2.4 hours;
(2) Heating the carbon powder obtained in the step (1) to 900 ℃ in steam at a speed of 75 ℃/h, and preserving heat for 48h to obtain an integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
The integrated desulfurization and decyanation catalysts in example 1 and comparative example 3 were subjected to an X-ray photoelectron spectroscopy nitrogen 1s peak test, which is as follows: x-ray photoelectron spectroscopy (ESCAlab 250, thermo, U.S.A.) using AlK alpha target (1486.6 eV), power of 150W, instrument resolution of 0.8eV (Ag 3d 5/2), analysis depth of 10 nm, single scanning energy of 40eV, background vacuum degree of 10 -8 Torr, the influence of the charge effect is subtracted by taking a carbon pollution peak C1s at 284.6eV as a calibration standard, the binding energy data error is +/-0.2 eV, the test result of the example 1 is shown in figure 1, and the test result of the comparative example 3 is shown in figure 2.
The integrated desulfurization and decyanation catalyst in the above examples and comparative examples was used to treat blast furnace gas at a temperature of about 120℃under a pressure of 250kPa and a flow rate of 54 ten thousand Nm 3 And/h. Detection of COS and H before and after treatment by gas chromatography (Shimadzu 2010 plus) 2 S concentration, the concentration of HCN before and after treatment was detected by an HCN concentration detector (SK-600), and the concentration of COS in the blast furnace gas before treatment was 150mg/m 3 ，H 2 S concentration is 70mg/m 3 HCN concentration is 300mg/m 3 To obtain the concentration of COS and H in the treated blast furnace gas 2 After the concentration of S and HCN are calculated, the hydrolysis efficiency and H of COS and HCN are obtained 2 The adsorption efficiency of S is shown in table 1;
TABLE 1
Figure SMS_1
Figure SMS_2
From table 1:
(1) The integrated desulfurization and decyanation catalyst in the embodiments 1 to 5 of the invention can realize the high-efficiency hydrolysis of COS and HCN and H 2 S is efficiently adsorbed, and the integrated desulfurization and decyanation catalyst realizes COS and H simultaneously 2 S and HCN are removed;
(2) As can be seen from the comparison between the embodiment 1 and the embodiment 6, the alkali modified activated carbon in the integrated desulfurization and decyanation catalyst is potassium hydroxide modified activated carbon, and the hydrolysis efficiency of COS and HCN is superior to that of the alkali modified activated carbon which is calcium hydroxide modified activated carbon, because the alkalinity of potassium hydroxide is stronger than that of calcium hydroxide, and pyridine and pyrrole functional groups which promote hydrolysis are more easily generated after the alkali modified activated carbon is combined with the activated carbon;
(3) As is clear from a comparison of example 1 and example 7, the desulfurization agent in the integrated desulfurization and decyanation catalyst of the present invention is ferric oxide, and the catalyst is specific to H 2 S has better adsorption efficiency than other desulfurizing agents such as zinc oxide, and the like, because ferric oxide can be subjected to regeneration reaction under the aerobic condition, and ferric iron after adsorption is changed into ferrous iron and can be used for oxidizing O of blast furnace gas 2 The intermediate oxidation is regenerated into ferric iron, so that the sulfur capacity of the integrated desulfurization and decyanation catalyst is improved;
(4) As is clear from a comparison of example 1 with examples 8 and 9, the mass ratio of carbon powder to alkali in the first mixture affects the hydrolysis efficiency of COS, HCN and H 2 S adsorption efficiency, when the mass ratio of carbon powder to alkali in the first mixture is low, the hydrolysis efficiency of COS and HCN is reduced, H 2 The adsorption efficiency of S is lowered due to collapse of catalyst channels caused by excessive alkali, and active sites are difficult to contact COS, HCN and H 2 S, the gas mass transfer efficiency is reduced; when the mass ratio of carbon powder to alkali in the first mixture is higher, the hydrolysis efficiency of COS and HCN is reduced, H 2 The adsorption efficiency of S is reduced, because the carbon powder is excessively high to cause insufficient alkalinity on the surface of the catalyst, pyridine and pyrrole functional groups for promoting the reaction are difficult to generate, the activity of an active site is reduced, and the efficiency is reduced;
(5) As is clear from a comparison of example 1 with examples 10 and 11, the mass ratio of the alkali-modified carbon powder to the desulfurizing agent in the second mixture affects the hydrolysis efficiency of COS, the hydrolysis efficiency of HCN, and H 2 S adsorption efficiency, when the mass ratio of alkali modified carbon powder to desulfurizing agent in the second mixture is lower, the hydrolysis efficiency of COS and HCN is reduced, H 2 S adsorption efficiency increases due to the increase in the proportion of desulfurizing agent to enhance H 2 S is adsorbed, but when the ratio of the desulfurizing agent exceeds a set value, COS and HCN are not subjected to hydrolysis reaction any more due to strong interaction of the desulfurizing agent, and are directly adsorbed by the desulfurizing agent, so that the catalyst is quickly deactivated due to poisoning; when the mass ratio of the alkali modified carbon powder to the desulfurizing agent in the second mixing is higher When the hydrolysis efficiency of COS and HCN is lowered, H 2 S has a reduced adsorption efficiency due to H caused by insufficient content of desulfurizing agent 2 S adsorption amount is reduced, part H 2 S is adsorbed on hydrolysis active sites to cause a great deal of deposition of sulfur on the surface of the catalyst, so that the hydrolysis reaction of COS and HCN is affected;
(5) As can be seen from the comparison between the embodiment 1 and the comparative example 1, the integrated desulfurization and decyanation catalyst is an alkali modified active carbon supported desulfurizing agent, and the hydrolysis efficiency of COS and the hydrolysis efficiency of HCN are superior to those of the integrated desulfurization and decyanation catalyst which is an active carbon supported desulfurizing agent, because the alkalinity of the active carbon is improved after alkali modification, the quantity of the surface such as pyridine and pyrrole is increased, and the adsorption strength of the COS and the HCN to acid gases such as COS and HCN is high, so that the hydrolysis reaction of the COS and the HCN is promoted;
(6) As can be seen from the comparison of example 1 and comparative example 2, the integrated desulfurization and decyanation catalyst in the invention is an alkali modified activated carbon supported desulfurization agent, for H 2 S has better adsorption efficiency than the integrated desulfurization and decyanation catalyst which is alkali modified active carbon, because the desulfurizing agent loaded on the surface of the alkali modified active carbon can improve H 2 S to sulfate conversion efficiency, thereby realizing H generated by COS hydrolysis reaction 2 S and H in furnace gas 2 S, removing;
(7) As is clear from the comparison between example 1 and comparative example 3, the integrated desulfurization and decyanation catalyst of the present invention is an alkali-modified activated carbon-supported desulfurizing agent, and has hydrolysis efficiency on COS, HCN and H 2 S has better adsorption efficiency than the integrated desulfurization and decyanation catalyst which is activated carbon; as can be seen from fig. 1 and 2, pyridine and/or pyrrole is formed on the surface of the activated carbon after alkali modification.
In conclusion, the integrated desulfurization and decyanation catalyst provided by the invention realizes COS and H simultaneously 2 S and HCN are removed, and H is removed 2 The influence on the removal efficiency of COS and HCN is reduced during S, so that the service life is longer, and the floor area of the blast furnace gas desulfurization and decyanation device can be reduced by using the integrated desulfurization and decyanation catalyst.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.

Claims (10)

1. The integrated desulfurization and decyanation catalyst is characterized by comprising alkali modified activated carbon and a desulfurizing agent loaded on the alkali modified activated carbon.
2. The integrated desulfurization and decyanation catalyst of claim 1, wherein the surface of the alkali modified activated carbon has pyridine and/or pyrrole;
preferably, the alkali modified activated carbon is any one or a combination of at least two of potassium hydroxide modified activated carbon, sodium hydroxide modified activated carbon and calcium hydroxide modified activated carbon, preferably potassium hydroxide modified activated carbon;
preferably, the desulfurizing agent comprises any one or a combination of at least two of a calcium-based desulfurizing agent, a sodium-based desulfurizing agent, an amino desulfurizing agent, a magnesium-based desulfurizing agent, or an iron-based desulfurizing agent;
preferably, the desulfurizing agent is ferric oxide;
preferably, the appearance shape of the integrated desulfurization and decyanation catalyst is cylindrical;
preferably, the height of the cylinder is 10-14 mm, and the diameter of the bottom surface is 8-10 mm.
3. A method for preparing the integrated desulfurization and decyanation catalyst as claimed in claim 1 or 2, characterized in that the preparation method comprises:
and (3) mixing the carbon powder with alkali to obtain alkali modified carbon powder, and activating the alkali modified carbon powder and the desulfurizing agent after mixing the alkali modified carbon powder and the desulfurizing agent to obtain the integrated desulfurization and decyanation catalyst.
4. The preparation method according to claim 3, wherein the mass ratio of carbon powder to alkali in the first mixture is 100 (8-12);
Preferably, the base comprises any one or a combination of at least two of potassium hydroxide, sodium hydroxide and calcium hydroxide, preferably potassium hydroxide;
preferably, the first mixing mode comprises first stirring, wherein the rotating speed of the first stirring is 50-60 r/s, the time is 3-5 h, and the temperature is 20-30 ℃;
preferably, the first mixing and the second mixing further comprise a first standing and a first cleaning which are sequentially carried out;
preferably, the first standing time is 3-5 hours;
preferably, the first washing comprises washing to a pH of 6.8 to 7.6.
5. The preparation method according to claim 3 or 4, wherein the mass ratio of the alkali modified carbon powder to the desulfurizing agent in the second mixture is 100 (5-9);
preferably, the second mixing mode comprises second stirring, wherein the rotation speed of the second stirring is 50-60 r/s, the time is 3-5 h, and the temperature is 20-30 ℃;
preferably, the second mixing and the activating further comprise a second standing and a second cleaning which are sequentially carried out;
preferably, the second standing time is 3-5 hours;
preferably, the second washing comprises washing to a pH of 6.8 to 7.6.
6. The method according to any one of claims 3 to 5, wherein the activation comprises heat treatment in steam;
Preferably, the heat treatment comprises sequentially heating and preserving heat;
preferably, the heating rate is 70-80 ℃/h, and the end temperature is 800-1000 ℃;
preferably, the time of heat preservation is 40-56 h.
7. The method according to any one of claims 3 to 6, wherein the method for producing carbon powder comprises:
sieving, drying, dehydrating, carbonizing and ball milling anthracite to obtain the carbon powder;
preferably, the temperature of the drying and dehydration is 100-140 ℃ and the time is 10-14 h;
preferably, the carbonization comprises a first carbonization heating, a second carbonization heating and carbonization heat preservation which are sequentially carried out in a protective atmosphere;
preferably, the heating rate of the first carbonization heating is 20-40 ℃/min, and the end point temperature is 350-450 ℃;
preferably, the temperature rising rate of the second carbonization temperature rising is 2-8 ℃/min, and the end point temperature is 500-600 ℃;
preferably, the carbonization heat preservation time is 1.5-3 hours;
preferably, the size of the carbon powder obtained after ball milling is 80-120 meshes.
8. The production method according to any one of claims 3 to 7, characterized in that the production method further comprises granulation after the activation;
Preferably, the pelletization results in cylindrical integrated desulfurization and decyanation catalyst particles.
9. The production method according to any one of claims 3 to 8, characterized in that the production method comprises:
(1) Sieving anthracite, drying and dehydrating at 100-140 ℃ for 10-14 h, carbonizing and ball milling to obtain the carbon powder with the size of 80-120 meshes, wherein the carbonizing comprises heating to 350-450 ℃ at the speed of 20-40 ℃/min in a protective atmosphere, heating to 500-600 ℃ at the speed of 2-8 ℃/min, and preserving heat for 1.5-3 h;
(2) Stirring and mixing carbon powder obtained in the step (1) with potassium hydroxide for 3-5 hours at the temperature of 20-30 ℃ at the rotating speed of 50-60 r/s for 100 (8-12) for 3-5 hours, standing for 3-5 hours, and cleaning until the pH value is 6.8-7.6 to obtain alkali modified carbon powder;
(3) And (3) at the temperature of 20-30 ℃, stirring and mixing the alkali modified carbon powder obtained in the step (2) with the mass ratio of 100 (5-9) for 3-5 hours at the rotating speed of 50-60 r/s, standing for 3-5 hours, cleaning to pH of 6.8-7.6, heating to 800-1000 ℃ in steam at the speed of 70-80 ℃/h, and preserving heat for 40-56 hours to obtain the integrated desulfurization and decyanation catalyst, and granulating to obtain cylindrical integrated desulfurization and decyanation catalyst particles.
10. Use of an integrated desulfurization and decyanation catalyst according to claim 1 or 2, characterized in that it is used for integrated desulfurization and decyanation of blast furnace gas.
CN202310208608.2A 2023-03-07 2023-03-07 Integrated desulfurization and decyanation catalyst and preparation method and application thereof Pending CN116371392A (en)

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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01143155A (en) * 1987-11-27 1989-06-05 Ishikawajima Harima Heavy Ind Co Ltd Fuel cell power generator
CN1095963A (en) * 1994-03-12 1994-12-07 湖北省化学研究所 Auto-vulcanization hydrogen, sulphur carbonoxide, carbon disulfide inversion absorption type desulfurizing agent and preparation
CA2453155A1 (en) * 2002-12-20 2004-06-20 Global Thermoelectric Inc. Propane desulphurization
CN101664689A (en) * 2009-09-16 2010-03-10 长春惠工净化工业有限公司 Active carbon desulfurizer and preparation method thereof
CN102500362A (en) * 2011-12-02 2012-06-20 中国科学院山西煤炭化学研究所 Catalyst for removing H2S from gas by catalytic oxidation, preparation method and application
CN103468338A (en) * 2013-09-12 2013-12-25 中国石油大学(北京) Ambient temperature fine desulfurization method of low-sulfur natural gas
CN104772146A (en) * 2015-03-18 2015-07-15 昆明理工大学 Preparation method of modified bio-charcoal based catalyst
CN107903949A (en) * 2017-11-15 2018-04-13 太原理工大学 A kind of coke oven gas desulfurization denitrogenation takes off the deep-purifying method of benzene hydrocarbon
CN111589415A (en) * 2020-05-14 2020-08-28 内蒙古浦瑞芬环保科技有限公司 Preparation method of active carbon loaded with zinc oxide in situ
CN111647445A (en) * 2020-07-03 2020-09-11 中国科学院过程工程研究所 Blast furnace gas integrated dry desulphurization device and process
CN111921363A (en) * 2020-06-27 2020-11-13 华东理工大学 High-efficiency desulfurizer for gas dry purification and preparation method and application thereof
CN112058273A (en) * 2020-08-26 2020-12-11 中国科学院山西煤炭化学研究所 Blast furnace gas desulfurization catalyst and preparation method and application thereof
CN113813946A (en) * 2021-10-26 2021-12-21 中冶赛迪上海工程技术有限公司 Desulfurizer doped with oxygen-containing functional group and preparation and application thereof
CN114057193A (en) * 2020-07-31 2022-02-18 宝山钢铁股份有限公司 Nitrogen-doped activated carbon-based desulfurizer as well as preparation method and application thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01143155A (en) * 1987-11-27 1989-06-05 Ishikawajima Harima Heavy Ind Co Ltd Fuel cell power generator
CN1095963A (en) * 1994-03-12 1994-12-07 湖北省化学研究所 Auto-vulcanization hydrogen, sulphur carbonoxide, carbon disulfide inversion absorption type desulfurizing agent and preparation
CA2453155A1 (en) * 2002-12-20 2004-06-20 Global Thermoelectric Inc. Propane desulphurization
CN101664689A (en) * 2009-09-16 2010-03-10 长春惠工净化工业有限公司 Active carbon desulfurizer and preparation method thereof
CN102500362A (en) * 2011-12-02 2012-06-20 中国科学院山西煤炭化学研究所 Catalyst for removing H2S from gas by catalytic oxidation, preparation method and application
CN103468338A (en) * 2013-09-12 2013-12-25 中国石油大学(北京) Ambient temperature fine desulfurization method of low-sulfur natural gas
CN104772146A (en) * 2015-03-18 2015-07-15 昆明理工大学 Preparation method of modified bio-charcoal based catalyst
CN107903949A (en) * 2017-11-15 2018-04-13 太原理工大学 A kind of coke oven gas desulfurization denitrogenation takes off the deep-purifying method of benzene hydrocarbon
CN111589415A (en) * 2020-05-14 2020-08-28 内蒙古浦瑞芬环保科技有限公司 Preparation method of active carbon loaded with zinc oxide in situ
CN111921363A (en) * 2020-06-27 2020-11-13 华东理工大学 High-efficiency desulfurizer for gas dry purification and preparation method and application thereof
CN111647445A (en) * 2020-07-03 2020-09-11 中国科学院过程工程研究所 Blast furnace gas integrated dry desulphurization device and process
CN114057193A (en) * 2020-07-31 2022-02-18 宝山钢铁股份有限公司 Nitrogen-doped activated carbon-based desulfurizer as well as preparation method and application thereof
CN112058273A (en) * 2020-08-26 2020-12-11 中国科学院山西煤炭化学研究所 Blast furnace gas desulfurization catalyst and preparation method and application thereof
CN113813946A (en) * 2021-10-26 2021-12-21 中冶赛迪上海工程技术有限公司 Desulfurizer doped with oxygen-containing functional group and preparation and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NURUL NORAMELYA ZULKEFLI ET AL., 《MOLECULES》 PERFORMANCE AND CHARACTERIZATION OF BI-METAL COMPOUND ON ACTIVATED CARBON FOR HYDROGEN SULFIDE REMOVAL IN BIOGAS, vol. 27, 17 December 2022 (2022-12-17), pages 1 - 16 *
刘伟强, 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 铁基复合型脱硫剂的制备及性能研究, no. 7, 15 July 2020 (2020-07-15), pages 13 *
耿朝阳, 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》负载铜、镍改性活性炭的制备及脱硫性能的研究, no. 1, 15 January 2018 (2018-01-15), pages 40 *

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