KR101806284B1 - A Method for Manufacturing Catalyst for Desulfurization in High Temperature Using Waste Magnesia - Google Patents

A Method for Manufacturing Catalyst for Desulfurization in High Temperature Using Waste Magnesia Download PDF

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KR101806284B1
KR101806284B1 KR1020150178569A KR20150178569A KR101806284B1 KR 101806284 B1 KR101806284 B1 KR 101806284B1 KR 1020150178569 A KR1020150178569 A KR 1020150178569A KR 20150178569 A KR20150178569 A KR 20150178569A KR 101806284 B1 KR101806284 B1 KR 101806284B1
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mixture
catalyst
desulfurization
pellet
high temperature
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KR1020150178569A
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Korean (ko)
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KR20170070717A (en
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이현
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재단법인 포항산업과학연구원
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    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • 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
    • B01J23/755—Nickel
    • 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
    • B01J37/082—Decomposition and pyrolysis

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The method for producing a high-temperature desulfurization catalyst using waste magnesia according to the present invention comprises the steps of: mixing nickel oxide and iron oxide at an equivalent ratio of 1: 1 to form a first mixture; Mixing 10-30 wt% of the first mixture and 90-70 wt% of pulverized magnesia powder to form a second mixture; Forming a spherical pellet using the second mixture; And heat-treating the pellet at a temperature of 1000 占 폚 or more for 2 hours or more in a hydrogen reducing atmosphere.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a catalyst for high temperature desulfurization using waste magnesia,

The present invention relates to a catalyst used for high-temperature desulfurization, and more particularly, to the production of a catalyst for high-temperature desulfurization which is excellent in high-temperature desulfurization performance using waste magnesia (MgO main component) refractory which is discarded after use in a steel process. The high temperature desulfurization catalyst of the present invention is used for decomposing and desulfurizing an organic component (C n H m ) such as benzene, toluene, xylene and naphthalene contained in an acid gas at a high temperature.

As a catalyst used for general desulfurization, gamma alumina is widely used, and active ions (active agent) are added to increase the catalyst efficiency. The impregnation method is widely used for the addition of active ions, and the impregnation method is a technique of dissolving a water-soluble salt in water to prepare an aqueous solution, and then impregnating the aqueous salt with gamma-alumina to add active ions.

A catalyst used for capturing H 2 S components in COG (Coke Oven Gas) generated in a coke oven at a high temperature to desulfurize the separated acid gas is proposed in Japanese Patent Application Laid-Open No. 1995-031878 do. This technique produces a catalyst by supporting a metal component having hydrogenation activity on a catalyst support containing alumina, magnesia and silica.

Japanese Patent Application Laid-Open No. 1997-164334 discloses a process for producing a polyolefin resin composition, which comprises 5 to 20% by weight of molybdenum converted into an oxide on a carrier of an inorganic oxide, and after drying and firing, another material such as nickel is added, A method for producing a catalyst is proposed.

Also, a method of removing sulfur compounds using a gas washing method in the form of a slurry mixed with water after pulverizing a desulfurization catalyst into a powder state is proposed in KR 1048425.

The desulfurization catalyst is subjected to a nitriding treatment, a calcination and a sulfidation treatment, nitriding the desulfurization catalyst with a nitriding agent at 400 to 800 캜, calcining at 300 to 700 캜, and then sulfidizing at 300 to 500 캜 with a sulfurizing agent, Is proposed in KR-0243833.

Meanwhile, in the present invention, a process for decomposing and desulfurizing an organic component including ammonia in a catalytic oven reactor is a desulfurization catalyst used at a high temperature because it has a high temperature of 1100 ° C or higher. However, the desulfurization catalyst prepared according to the prior art, in which the nickel compound is supported on the magnesia and is heat-treated at a low temperature of 800 ° C or lower to cause the nickel component to act as the active component in the magnesia, is deteriorated due to the high- There was a problem.

Therefore, in order to solve such problems in the present invention, a catalyst for high temperature desulfurization using a magnesia of waste refractory of steel industry has been developed and developed at a high temperature.

Japanese Unexamined Patent Publication No. 7-31878 Japanese Patent Application Laid-Open No. 9-164334 Korean Patent No. 1048425 Korean Patent No. 0243833

In the present invention, a desulfurization treatment process is a method of producing a catalyst for high-temperature desulfurization using waste magnesia which can increase stability at a high temperature and increase desulfurization efficiency, compared with a conventional catalyst for desulfurization showing a tendency that a remarkable desulfurization yield tends to decrease at a high temperature of 1100 ° C or higher .

One embodiment of the present invention is a method for manufacturing a nickel-chromium alloy, comprising: mixing nickel oxide and iron oxide in an equivalent ratio of 1: 1 to form a first mixture; Mixing 10-30 wt% of the first mixture and 90-70 wt% of pulverized magnesia powder to form a second mixture; Forming a spherical pellet using the second mixture; And heat treating the pellets at a temperature of 1000 占 폚 or higher for 2 hours or longer in a hydrogen reducing atmosphere. The present invention also provides a method for producing a catalyst for high temperature desulfurization using waste magnesia.

The method may further comprise adding moisture to the first mixture.

The step of forming the pellet may be a step of ball milling the second mixture, mixing and pulverizing the same, drying and forming the pellet into a pelletizer to produce a spherical pellet.

The step of forming the pellet may include milling for 6 hours or more using a ball mill.

The method may further comprise adding moisture to the second mixture.

As described above, the high temperature desulfurization catalyst produced using the mixture of nickel oxide and iron oxide and the waste magnesia produced according to the present invention has a high thermal stability and a high effect of high temperature desulfurization. Further, due to the high temperature stability, when the organic component and ammonia contained in the desulfurized gas are contained, even if the temperature rises due to the high-temperature exothermic phenomenon, a normal desulfurizing effect can be exhibited.

In addition, since thermal stability is ensured when used for reforming reaction, exhaust gas treatment, and high-temperature desulfurization, the lifetime of the catalyst is extended, and the cost for replacing the catalyst can be reduced due to a long lifetime.

1 shows the desulfurization conversion (%) according to the weight percentage of the combination of nickel oxide and iron oxide.

The specific structure or functional description presented in the embodiment of the present invention is merely illustrative for the purpose of illustrating an embodiment according to the concept of the present invention, and embodiments according to the concept of the present invention can be implemented in various forms. Also, it should be understood that the present invention should not be construed as limited to the embodiments described herein, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention. Hereinafter, the present invention will be described in detail with reference to the drawings.

In order to achieve the above object, the present invention provides a method for preparing a catalyst for high-temperature desulfurization using waste magnesia, comprising: mixing nickel oxide and iron oxide in an equivalent ratio of 1: 1 to form a first mixture; Mixing 10-30 wt% of the first mixture and 90-70 wt% of pulverized magnesia powder to form a second mixture; Forming a spherical pellet using the second mixture; And heat-treating the pellet at a temperature of 1000 占 폚 or more for 2 hours or more in a hydrogen reducing atmosphere.

In the case of a general catalyst, since the catalyst is present only on the surface of the catalyst, the active catalyst is volatilized on the surface at the time of prolonged use to decrease or lose the catalyst powder component in powder state. And the performance is remarkably lowered.

In the present invention, nickel oxide and iron oxide are mixed from the beginning and mixed with waste magnesia powder to prepare a catalyst so that such phenomenon does not occur. Thus, when the catalyst of the present invention is used for desulfurization at a high temperature by allowing the nickel and iron components to exhibit crystal structure on the surface of the magnesia powder, the organic component contained in the acid gas is decomposed on the surface of the catalyst, To improve and improve the effect suited to the condition.

Further, spherical pellets are formed using the second mixture, and then heat-treated in a hydrogen reducing atmosphere at 1000 ° C or more for 2 hours or more. The reduction heat treatment produces metal nickel and metal iron in the reduced state on the magnesia surface and forms active sites of nickel and iron to improve the performance of the catalyst. In addition, a part of nickel ferrite (Ni ferrite) is formed on the surface of the magnesia powder to maintain the performance even when the catalyst deteriorates.

However, when the heat treatment temperature is lower than 1000 ℃, the reduced catalyst exhibits poor performance and some nickel ferrite formation is observed to be insufficient. Therefore, in the present invention, it is preferable to heat-treat spherical pellets in a hydrogen reducing atmosphere at a temperature of 1000 DEG C or higher.

It is also possible to control the amount of nickel ferrite in accordance with the heat treatment time. In the present invention, the heat treatment time is preferably 2 hours or more. More preferably, the heat treatment time is within 2 hours to 5 hours.

The composition of the waste magnesia used in the present invention is shown in Table 1.

ingredient MgO Al 2 O 3 Fe 2 O 3 SiO 2 CaO Na 2 O + K 2 O Lung magnesia
(weight%) 82-90 0.8-2.5 0.8-1.5 2.1-4.5 1.5-2.8 0.5-1.5

Further, in the production method of the present invention, it is preferable that 10-30% by weight of the first mixture and 90-70% by weight of pulverized magnesia powder are mixed to form a second mixture. The reason for this is that when the magnesia used as a carrier at a high temperature is 70% by weight or more, high temperature stability is good. In addition, since the catalytic performance is satisfactorily set so that at least 10% of the active component of the cocatalyst is contained, nickel oxide and iron oxide are mixed so as to have an equivalent ratio of 1: 1, and 10-30% by weight of this mixture and the waste magnesia powder 90 -70% by weight is preferable.

According to an embodiment of the present invention, the method for producing a catalyst for high-temperature desulfurization using waste magnesia of the present invention may further comprise adding moisture to the first mixture. In this case, a slurry is formed, and 10-30% by weight of the slurry and 90-70% by weight of pulverized magnesia powder are mixed to form a second mixture.

Further, the pellet forming step is by a conventional technique, and is not limited to any specific method. For example, the second mixture is ball-milled, mixed and crushed, dried and molded into a pelletizer to produce spherical pellets.

Preferably, the milling time using a ball mill may be at least 6 hours. When the catalyst is pulverized for more than 6 hours, the specific surface area increases as the surface is pulverized, which promotes the catalytic activity by homogenizing the characteristics of the catalyst. Also, the reactivity is improved on the magnesia surface, and the catalytic effect is enhanced.

In producing the catalyst for desulfurization of the present invention, it is preferable to use a pellet molding machine. In the pellet molding machine, uniform spherical particles can be produced by using a rotary disk. The size of the spherical particles is preferably adjusted to various sizes depending on the shape and size of the reactor to be used. The preferred spherical particle size in the present invention is 0.5 mm to 30 mm.

The method for producing a catalyst for high-temperature desulfurization using waste magnesia according to the present invention may further comprise the step of adding water to the second mixture. In this case, a slurry is formed. The slurry is ball-milled, mixed and ground, dried, and molded into a pelletizer to form spherical pellets.

Hereinafter, the present invention will be described in detail with reference to examples.

[Example]

In this embodiment, in order to determine the ratio between the amount of waste magnesia and the amount of nickel oxide and iron oxide used, the weight of nickel oxide and iron oxide mixed at an equivalent ratio of 1: 1 is increased from 5% to 5% by 35% Magnesia was mixed. At this time, since the molecular weight of nickel oxide was 74.67 g and the molecular weight of iron oxide was 159.69 g, the weight ratio was 0.468 based on one-to-one equivalents. Seven kinds of pellets for practical use were prepared.

[Experimental Example 1]

The prepared 2 mm pellets were subjected to reduction treatment in a hydrogen atmosphere at 1000 ° C to prepare catalysts for high temperature desulfurization. In order to perform desulfurization performance test of 7 samples of each of the manufactured samples, 150 g of each of the prepared catalysts for high temperature desulfurization was installed in a tube furnace. H 2 S gas and SO 2 gas were mixed at a molar ratio of 2: 1, and the mixed gas was introduced at a rate of 30 ml / min to confirm the steady state. Thereafter, the components of the exhaust gas after the reaction were analyzed by gas chromatography, and the sum of H 2 S and SO 2 was calculated as a percentage after initial comparative treatment, and the results are shown in FIG.

As shown in FIG. 1, the desulfurization conversion rate is 90% or more at 10% to 30% of the nickel oxide and iron oxide weight percent, and the desulfurization conversion rate is 85% at 5% or less. In addition, since the desulfurization conversion rate tends to decrease to less than 89% at 35%, the present invention requires that the sum of the contents of nickel oxide and iron oxide be at least 10% and at most 30% And the remainder was made to be pulmonary magnesia.

[Experimental Example 2]

The experiment was carried out to derive conditions for hydrogen reduction heat treatment of the mixed pellet compacts. A pellet of waste magnesia was prepared in the same manner as in the above example except that the mixing weight of nickel oxide and iron oxide was 1: 1 and 20 wt%, respectively. The high temperature desulfurization catalysts were prepared by heating the four pellets for practical use at different temperatures from 900 ° C. to 1200 ° C. at intervals of 100 ° C. for 2 hours each.

The formation of nickel ferrite on the catalyst was confirmed according to the heat treatment condition of the high temperature desulfurization catalyst, and the change in the thermogravimetry was also measured. The thermogravimetric change was measured by weighing 0.5 g of the weight loss in the thermo-analyzer, and the results are shown in Table 2.

Heat treatment temperature (캜) Change in thermal weight (% reduction) XRD analysis confirmed the formation of nickel ferrite 900 0.7 NiO, Fe 2 O 3 single phase 1000 0.08 NiO, Fe 2 O 3 single phase, Ni ferrite phase containing 1100 0.03 NiO, Fe 2 O 3 single phase, Ni ferrite phase containing 1200 0.01 NiO, Fe 2 O 3 single phase, Ni ferrite phase containing

Referring to Table 2, it can be seen that the crystal phase structure is changed according to the heat treatment temperature, and the formation of nickel ferrite phase is observed when the heat treatment is performed at a temperature of 1000 to 1200 ° C. The formation of the nickel ferrite increases the desulfurization effect.

The heat treatment at a temperature of 1000 占 폚 or more is preferable because the change of the thermal weight is less than 0.1% under the condition of 1000 占 폚 or more. . It is also confirmed that the effect of reducing the thermal weight is excellent in the heat treatment condition of 1000 ° C. or more, which is consistent with the formation temperature of the nickel ferrite.

Claims (5)

Mixing nickel oxide and iron oxide in an equivalent ratio of 1: 1 to form a first mixture;
Mixing 10-30 wt% of the first mixture and 90-70 wt% of pulverized magnesia powder to form a second mixture;
Adding moisture to the second mixture;
Forming a spherical pellet using the second mixture; And
And heat-treating the pellet at a temperature of 1000 占 폚 or higher for 2 hours or longer in a hydrogen reducing atmosphere.
The method according to claim 1,
Wherein the method further comprises adding water to the first mixture. ≪ RTI ID = 0.0 > 8. < / RTI >
The method according to claim 1,
Wherein the step of forming the pellet is a step of ball-milling the second mixture, mixing and pulverizing the same, drying and forming a spherical pellet by a pelletizer, wherein the spherical pellet is formed.
The method of claim 3,
Wherein the step of forming the pellet comprises grinding a ball mill using a ball mill for 6 hours or more.
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KR1020150178569A 2015-12-14 2015-12-14 A Method for Manufacturing Catalyst for Desulfurization in High Temperature Using Waste Magnesia KR101806284B1 (en)

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KR101048425B1 (en) * 2010-07-28 2011-07-11 조명호 Desulfuring catalyst and method for preparing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101048425B1 (en) * 2010-07-28 2011-07-11 조명호 Desulfuring catalyst and method for preparing the same

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