CN114570434A - Honeycomb body forming catalyst and preparation method and application thereof - Google Patents

Honeycomb body forming catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114570434A
CN114570434A CN202011372709.6A CN202011372709A CN114570434A CN 114570434 A CN114570434 A CN 114570434A CN 202011372709 A CN202011372709 A CN 202011372709A CN 114570434 A CN114570434 A CN 114570434A
Authority
CN
China
Prior art keywords
catalyst
oxide
drying
roasting
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011372709.6A
Other languages
Chinese (zh)
Inventor
李子宜
刘应书
张璇
姜理俊
杨雄
刘梦溪
刘文海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongke Huizhi (Dongguan) Equipment Technology Co.,Ltd.
Original Assignee
Zhongda Huizhiyuanchuang Beijing Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhongda Huizhiyuanchuang Beijing Technology Co ltd filed Critical Zhongda Huizhiyuanchuang Beijing Technology Co ltd
Priority to CN202011372709.6A priority Critical patent/CN114570434A/en
Publication of CN114570434A publication Critical patent/CN114570434A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a honeycomb body forming catalyst, a preparation method and application thereof, wherein the preparation method of the honeycomb body forming catalyst comprises the following steps: mixing the catalyst raw powder with a binder, a peptizing agent, an extrusion aid, a pore-forming agent and a forming aid to form a mixture; adding water into the mixture, uniformly mixing, kneading, aging, extruding, molding, drying and roasting in sequence; the drying is sectional drying, each section of drying keeps constant temperature and humidity, the humidity keeps 50-90 wt%, and the roasting is sectional roasting. The preparation method of the honeycomb-shaped catalyst provided by the invention obviously improves the stability and compressive property of the catalyst, and the catalyst is well applied to the aspect of CO catalysis.

Description

Honeycomb body forming catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of CO catalysis, in particular to a honeycomb body forming catalyst and a preparation method and application thereof.
Background
The CO content of the steel sintering flue gas is high, and the concentration can reach 6000 to 20000ppm (7500 to 25000 mg/m)3) However, at present, no specific purification means or specific environmental protection indexes and supervision measures are available for emission reduction control of sintering flue gas CO. Direct evacuation of flue gas CO leads to generally higher levels of CO concentration in the ambient atmosphere inside and in the relevant areas of the steel mill. CO is a highly toxic gas, and when the content of CO in the air reaches 12000ppm, the CO can cause death within 1-3 min. The national design and health Standard of Industrial enterprises (TJ 36-1979) requires that the maximum allowable CO concentration of harmful substances in the atmosphere of residential areas is 3.00mg/m3(2.4ppm, first order value); grading of occupational exposure toxicant hazard degree (GBZ 230-2010) with maximum allowable concentration of CO of 20mg/m in occupational exposure limit3(16ppm)。
The development of a high-efficiency purification and removal technology for CO in the sintering flue gas is urgent. The sintering flue gas flow is large (100-200 ten thousand Nm)3H), low temperature (50-130 deg.C), high humidity (RH)>90%), complex composition, high efficiency and limited adaptation of CO purification techniques. Among the methods, based on promoting CO and O in flue gas2(concentration about 15%) is converted to CO2The low-temperature catalytic oxidation method based on the principle is favored due to the characteristics of high purification efficiency, low operation temperature, easy operation, environmental friendliness and the like. However, long-term catalyst application practices have demonstrated that lower operating temperatures result in lower catalytic efficiencies, high humidity results in severe deactivation of the common noble or non-noble metal-based catalysts, and complex flue gas constituents further exacerbate the rate of catalyst deactivation. In addition, large flow of flue gas can occupy the space in limited catalyst fillingUnder the intermediate condition, larger wind resistance is caused, and the energy consumption of the fan is improved; prolonged impingement with relatively high velocity gas streams can cause dusting of the formed catalyst which can cause plugging problems when blown into the tubes. Therefore, the method can keep the catalytic activity and the mechanical property of the catalyst stable for a long time under the severe condition of the sintering flue gas, and simultaneously solve the engineering problems of energy consumption, land occupation, pipeline blockage and the like, thereby becoming the biggest challenge in the application of the current sintering flue gas CO low-temperature catalytic oxidation technology.
In the selective oxidation reaction of carbon monoxide, noble metal systems such as gold, platinum and rhodium are studied more frequently, but the development of the catalysts is limited due to limited reserves and higher cost. At present, the catalyst is widely used for purifying CO mainly by a hopcalite particle catalyst and an integral catalyst of noble metals such as platinum, palladium and the like. The hopcalite catalyst is extremely afraid of water, and a large amount of drying agent is needed to be used; the platinum and palladium noble metal monolithic catalyst has good water resistance, but has high cost, the use temperature generally needs more than 300 ℃, and the noble metal is easy to sinter and deactivate. The catalyst has excellent catalytic activity and stability, but is expensive; non-noble metal carbon monoxide catalysts are mainly hopcalite agents, and a large amount of hopcalite catalysts are generally placed in ventilation pipelines for carbon monoxide gas purification in mine refuge chambers and other closed spaces, so that the purification mode has extremely low carbon monoxide purification efficiency and causes catalyst waste. Therefore, the research on the non-noble metal monolithic catalyst for purifying the carbon monoxide has important social significance.
In addition, the traditional CO oxidation catalyst carriers are all powder particles, so that the catalyst has the following defects that (1) the loading and unloading are troublesome; (2) is not easy to form and the mechanical strength can not meet the requirement; (3) mass and heat transfer are greatly hindered, and the treatment efficiency is reduced; (4) the pressure drop difference between the front and the back of the catalyst bed is large, and the energy consumption is increased.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a honeycomb formed catalyst, which is a catalyst with a monolithic bed honeycomb structure, and overcomes the defects (large airflow pressure resistance, high energy consumption of a required blower, insufficient mechanical strength of catalyst particles, easy pulverization and the like) caused by the adoption of the traditional particulate catalyst, and has excellent stability and catalytic effect.
The second objective of the present invention is to provide a method for preparing the above honeycomb shaped catalyst, which significantly improves the stability, pressure resistance and catalytic effect of the catalyst itself by means of multi-stage calcination and multi-stage drying.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a honeycomb body forming catalyst which is mainly prepared by taking manganese oxide and copper oxide as main components and other metal oxides as auxiliary components; wherein the mass ratio of the copper oxide to the manganese oxide to the other metal oxides is (5-50): (50-90): (1-10).
The catalyst belongs to an integral catalyst, overcomes a plurality of defects of a granular structure catalyst in the prior art, and improves the catalytic effect of the catalyst through effective proportioning of active ingredients of the catalyst.
Preferably, in the honeycomb shaped catalyst of the present invention, the other metal oxide may include any one or more of cerium oxide, tin oxide, cobalt oxide, lanthanum oxide, praseodymium oxide, samarium oxide, europium oxide, gadolinium oxide, potassium oxide, calcium oxide, zinc oxide, magnesium oxide, and nickel oxide. The metal oxide improves the catalytic effect of the monolithic catalyst by matching with main components such as manganese oxide, copper oxide and the like.
In order to solve the problems of the granular catalyst in use and optimize heterogeneous catalytic reaction, the invention provides a monolithic catalyst which has the performances and characteristics of both a catalyst and a reactor, and has the following advantages compared with the granular catalyst: 1) the local porosity of the catalyst bed layer is uniformly distributed; 2) the pressure drop of the catalyst bed layer is low; 3) the mass transfer rate is high, and the reaction is rapid; 4) the activity and the selectivity of the catalyst are high; 5) the powder is not easy to be pulverized; 6) the mechanical strength is high, and the stability is strong; 7) the catalyst is easy to assemble and disassemble, the reactor is easy to maintain, the operation cost is reduced, and the whole formed honeycomb catalyst is composed of the catalyst, so that the catalyst efficiency is improved.
The invention provides a honeycomb shaped catalyst product and a preparation method of the honeycomb shaped catalyst, which comprises the following steps:
mixing the catalyst raw powder with a binder, a peptizing agent, an extrusion aid, a pore-forming agent and a forming aid to form a mixture;
adding water into the mixture, uniformly mixing, kneading, aging, extruding, molding, drying and roasting in sequence;
the drying is sectional drying, each section of drying keeps constant temperature and humidity, the humidity is kept at 50-90%, and the roasting is sectional roasting.
The inventor finds that the monolithic catalyst has problems in practical application through long-term practice, and the catalyst has poor activity and stability, particularly poor pressure resistance.
Therefore, in order to solve the above technical problems, the present invention provides a method for preparing a honeycomb formed catalyst, which improves the stability of the catalyst itself, reduces the falling rate, and makes the catalyst powder more uniform by means of segmented drying and segmented calcination. The constant temperature and humidity of the environment need to be ensured in the drying process, and the constant temperature and humidity state needs to be maintained so as to reduce cracking in the catalyst forming process and improve the stability of the catalyst.
Preferably, the mass of the raw catalyst powder is 40-80 wt% of the mass of the mixture, and the catalytic effect of the prepared molded catalyst is ensured by controlling the content of the raw catalyst powder in a proper amount. Preferably, in the process of adding water into the mixture and uniformly mixing, the mass of the added water is 0.5-1.5 times of the mass of the mixture, and the mixture is uniformly dispersed by matching with a proper amount of water. Preferably, the number of the sections in the drying process is 2-10, the drying temperature of the section 1 is 15-20 ℃, the temperature of each subsequent section is 10-15 ℃ higher, and the drying temperature of the last section is 100-110 ℃.
In the concrete actual operation, the two-stage, three-stage, four-stage, five-stage, six-stage, seven-stage, eight-stage, nine-stage and ten-stage drying process is respectively operated according to the following modes:
and (2) second stage: drying at 20 ℃ until the water content is less than 10 wt%, and slowly heating the blank to 110 ℃ until the blank is completely dried;
and (3) three stages: drying at 20 ℃ until the moisture content is less than 20 wt%, slowly heating the embryo body to 30 ℃ for drying until the moisture content is less than 10 wt%, and slowly heating the embryo body to 110 ℃ until the embryo body is completely dried;
and a fourth stage: drying at 20 ℃ until the moisture content is less than 30 wt%, slowly heating the embryo body to 30 ℃ for drying until the moisture content is less than 20 wt%, slowly heating the embryo body to 40 ℃ for drying until the moisture content is less than 10 wt%, and slowly heating the embryo body to 110 ℃ until the embryo body is completely dried;
five stages: firstly, drying at 20 ℃ until the moisture content is less than 40 wt%, slowly heating the embryo body to 30 ℃ for drying, slowly heating the embryo body to 40 ℃ for drying after the moisture content is less than 30 wt%, slowly heating the embryo body to 50 ℃ for drying after the moisture content is less than 20 wt%, and slowly heating the embryo body to 110 ℃ until the embryo body is completely dried after the moisture content is less than 10 wt%;
six sections: firstly, drying at 20 ℃ until the moisture content is less than 50 wt%, slowly heating the embryo body to 30 ℃ for drying until the moisture content is less than 40 wt%, slowly heating the embryo body to 40 ℃ for drying until the moisture content is less than 30 wt%, slowly heating the embryo body to 50 ℃ for drying until the moisture content is less than 20 wt%, slowly heating the embryo body to 60 ℃ for drying until the moisture content is less than 10 wt%, and slowly heating the embryo body to 110 ℃ until the embryo body is completely dried;
seven sections: firstly, drying at 20 ℃ until the moisture content is less than 60 wt%, slowly heating the blank to 30 ℃ for drying until the moisture content is less than 50 wt%, slowly heating the blank to 40 ℃ for drying until the moisture content is less than 40 wt%, slowly heating the blank to 50 ℃ for drying until the moisture content is less than 30 wt%, slowly heating the blank to 60 ℃ for drying until the moisture content is less than 20 wt%, slowly heating the blank to 70 ℃ for drying until the moisture content is less than 10 wt%, and slowly heating the blank to 110 ℃ until the blank is completely dried;
eight sections: firstly, drying at 20 ℃ until the moisture content is less than 70 wt%, slowly heating the blank to 30 ℃ for drying until the moisture content is less than 60 wt%, slowly heating the blank to 40 ℃ for drying until the moisture content is less than 50 wt%, slowly heating the blank to 50 ℃ for drying until the moisture content is less than 40 wt%, slowly heating the blank to 60 ℃ for drying until the moisture content is less than 30 wt%, slowly heating the blank to 70 ℃ for drying until the moisture content is less than 20 wt%, slowly heating the blank to 80 ℃ for drying until the moisture content is less than 10 wt%, and slowly heating the blank to 110 ℃ until the blank is completely dried;
nine sections: firstly, drying at 20 ℃ until the moisture content is less than 80 wt%, slowly heating the blank to 30 ℃ for drying until the moisture content is less than 70 wt%, slowly heating the blank to 40 ℃ for drying until the moisture content is less than 60 wt%, slowly heating the blank to 50 ℃ for drying until the moisture content is less than 50 wt%, slowly heating the blank to 60 ℃ for drying until the moisture content is less than 40 wt%, slowly heating the blank to 70 ℃ for drying until the moisture content is less than 30 wt%, slowly heating the blank to 80 ℃ for drying until the moisture content is less than 20 wt%, slowly heating the blank to 90 ℃ for drying until the moisture content is less than 10 wt%, and slowly heating the blank to 110 ℃ until the moisture content is completely dried;
ten sections: drying at 20 deg.C until the water content is less than 90 wt%, slowly heating the embryo body to 30 deg.C for drying until the water content is less than 80 wt%, slowly heating the embryo body to 40 deg.C for drying until the water content is less than 70 wt%, slowly heating the embryo body to 50 ℃ for drying until the water content is less than 60 wt%, slowly heating the embryo body to 60 ℃ for drying until the water content is less than 50 wt%, slowly heating the embryo body to 70 ℃ for drying until the water content is less than 40 wt%, slowly heating the embryo body to 80 ℃ for drying until the water content is less than 30 wt%, slowly heating the embryo body to 90 ℃ for drying until the water content is less than 20 wt%, slowly heating the embryo body to 100 ℃ for drying until the moisture content is less than 10 wt%, and slowly heating the embryo body to 110 ℃ until the drying is complete.
Preferably, the number of the sections in the roasting process is 2-4, the temperature rise rate of each section of the first 1-3 sections is controlled to be 0.5-2 ℃/min, the temperature is controlled to be 200-300 ℃, the roasting time is 2-12 h, the temperature rise rate of the last section is controlled to be 2-10 ℃/min, the temperature is controlled to be 400-700 ℃, and the roasting time is 2-12 h.
During the specific operation, the actual two-stage, three-stage and four-stage roasting process is carried out according to the following operations:
and (2) second stage: heating the mixture from room temperature to 200-300 ℃ at a speed of 0.5-2 ℃/min, roasting for 2-12 h, heating the mixture to 300-700 ℃ at a speed of 2-10 ℃/min, roasting for 2-12 h, and gradually cooling to room temperature after roasting is finished.
And (3) three stages: heating the mixture from room temperature to 200-300 ℃ at a speed of 0.5-2 ℃/min, roasting for 2-12 h, heating the mixture to 300-400 ℃ at a speed of 0.5-2 ℃/min, roasting for 2-12 h, heating the mixture to 400-700 ℃ at a speed of 2-10 ℃/min, and gradually cooling to room temperature after roasting.
And a fourth stage: heating from room temperature to 100-200 ℃ at the speed of 0.5-2 ℃/min, roasting for 2-12 h, heating to 200-300 ℃ at the speed of 0.5-2 ℃/min, roasting for 2-12 h, heating to 300-400 ℃ at the speed of 0.5-2 ℃/min, roasting for 2-12 h, heating to 400-700 ℃ at the speed of 2-10 ℃/min, roasting for 2-12 h, and gradually cooling to room temperature after roasting.
Preferably, the binder accounts for 10-50 wt% of the mass of the mixture;
the binder is any one or more of marble glue, AB glue, starch, polyvinyl alcohol, kaolin, hydrotalcite, silica sol, sodium silicate, alumina sol, polyacrylamide, methyl cellulose, sodium carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, corn oil, carboxypropyl methyl cellulose, tall oil, sodium stearate, starch, aluminum dihydrogen phosphate solution, aluminosilicate, pseudo-boehmite, mullite fiber, spodumene, eucryptite, ammonium methyl cellulose, asphalt, coal tar and cellulose.
Preferably, the peptizing agent accounts for 1-15 wt% of the mass of the mixture;
the type of the peptizing agent is any one or more of nitric acid, hydrochloric acid, acetic acid, formic acid, citric acid, trichloroacetic acid and malonic acid;
preferably, the extrusion aid is 1-15 wt% of the mass of the mixture;
the type of the extrusion aid is any one or more of sesbania powder, glycerol, salad oil, oxalic acid, tartaric acid, citric acid, polyacrylamide, stearic acid, glycerol, corn oil, tall oil, sodium stearate, palm oil, soybean oil, castor oil and acetic acid.
Preferably, the pore-forming agent accounts for 1-10 wt% of the mass of the mixture;
the pore-forming agent is any one or more of activated carbon, wood chips, kapok, starch, polyethylene glycol, urea, cellulose, polyoxyethylene, sesbania powder and sponge.
Preferably, the forming aid accounts for 0.1-5 wt% of the mass of the mixture;
the forming auxiliary agent comprises any one or more of glass fiber, pulp fiber, lactic acid and ethanolamine.
The forming degree and stability of the monolithic catalyst are improved by optimizing the types and the addition of the auxiliary agents in the forming process.
The honeycomb body forming catalyst has strong application in the aspect of CO catalytic oxidation in the field of sintering flue gas, and can reduce the CO concentration of steel sintering flue gas to be less than or equal to 1000ppm at 130 ℃.
The CO content of the sintering flue gas is generally 6000-8000 ppm, the flue gas temperature after dust removal, desulfurization and denitration is about 130 ℃, and the flue gas contains N2\O2\CO2\H2O, and small amount of SO2\NOx\NH3\Cl2And the like. The aim of the final purification is to reduce the CO content from 6000-8000 ppm to less than or equal to 1000 ppm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention improves the catalytic effect of the catalyst by reasonably proportioning the active ingredients and simultaneously improves the stability of the catalyst.
(2) The invention improves the stability and the pressure resistance of the catalyst by means of sectional drying and sectional roasting, reduces the falling rate and ensures that the catalyst powder is more uniform.
(3) The honeycomb body forming catalyst has stronger application effect and can be used at the airspeed of 200000h-1And when the temperature is 110-150 ℃, the concentration of CO in the steel sintering flue gas is reduced to be less than or equal to 1000ppm, and the method has good stability and can keep high purification efficiency for a long time.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a graph of the change in catalytic efficiency of a honeycomb shaped catalyst provided in accordance with example 1 of the present invention as a function of temperature.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the honeycomb shaped catalyst comprises the following steps:
1) preparing 80 wt% of catalyst powder, 10 wt% of carboxymethyl cellulose, 7 wt% of sesbania powder, 1 wt% of activated carbon, 1 wt% of glass fiber and 1 wt% of dilute nitric acid into a paste, wherein the active ingredients of the catalyst powder are copper oxide, manganese oxide and other metal oxides, and the mass ratio of the copper oxide to the manganese oxide is 50: 90: 1, the other metal oxide is a mixture of tin oxide, cobalt oxide and lanthanum oxide;
2) adding water with half mass of the mixture into the pug, uniformly mixing, transferring into a kneader, and stirring for 60min at 36 revolutions per minute to uniformly mix the pug;
3) and tightly packaging the pug with a preservative film, and aging for 24 hours under the conditions that the ambient temperature is 20 ℃ and the ambient humidity is 50%.
4) Putting the aged pug into a bar extruder to be pressed to generate a honeycomb-shaped formed catalyst; the extrusion pressure was 20 MPa.
5) And (3) secondary drying: drying at 20 ℃ in a constant temperature and humidity box with the humidity of 50% until the moisture content is less than 10 wt%, and slowly heating the embryo body to 110 ℃ until the embryo body is completely dried; the catalyst is turned over at regular time in the drying process to ensure that the integrity of the catalyst is good.
6) And (3) secondary roasting: heating from room temperature to 300 deg.C at 0.5 deg.C/min, roasting for 12 hr, heating to 400 deg.C at 2 deg.C/min, roasting for 2 hr, and cooling to room temperature.
Example 2
The preparation method of the honeycomb shaped catalyst comprises the following steps:
1)40 wt% of catalyst powder, 50 wt% of carboxymethyl cellulose, 1 wt% of sesbania powder, 3 wt% of activated carbon, 5 wt% of glass fiber and 1 wt% of dilute nitric acid, wherein the active ingredients of the catalyst powder are copper oxide, manganese oxide and other metal oxides, and the mass ratio of the copper oxide to the manganese oxide is 5: 50: 10, the other metal oxide is a mixture of praseodymium oxide, samarium oxide, europium oxide, gadolinium oxide, potassium oxide and calcium oxide;
2) adding water with the mass being 1 time of that of the mixture into the pug, uniformly mixing, transferring the mixture into a kneader, and stirring for 60min at 36 revolutions per minute to uniformly mix the pug;
3) and tightly packaging the pug with a preservative film, and aging for 24 hours under the conditions that the ambient temperature is 20 ℃ and the ambient humidity is 50%.
4) Putting the aged pug into a bar extruder to be pressed to generate a honeycomb-shaped formed catalyst; the extrusion pressure was 20 MPa.
5) And (4) four-stage drying: firstly, drying at 20 ℃, drying in a constant temperature and humidity box with the humidity of 60% until the moisture content is less than 30 wt%, slowly heating the embryo body to 30 ℃ for drying, drying until the moisture content is less than 20 wt%, slowly heating the embryo body to 40 ℃ for drying, drying until the moisture content is less than 10 wt%, and slowly heating the embryo body to 110 ℃ until the embryo body is completely dried; the catalyst is turned over at regular time in the drying process to ensure that the integrity of the catalyst is good.
6) Four-stage roasting: heating from room temperature to 100 deg.C at 2 deg.C/min, calcining for 2h, heating from 1 deg.C/min to 200 deg.C, calcining for 10h, heating from 0.5 deg.C/min to 400 deg.C, calcining for 5h, heating from 10 deg.C/min to 700 deg.C, and cooling to room temperature.
Example 3
The preparation method of the honeycomb shaped catalyst comprises the following steps:
1) preparing 58.9 wt% of catalyst powder, 10 wt% of carboxymethyl cellulose, 15 wt% of sesbania powder, 1 wt% of activated carbon, 0.1 wt% of glass fiber and 15 wt% of dilute nitric acid into a paste, wherein the active ingredients of the catalyst powder are copper oxide, manganese oxide and other metal oxides, and the mass ratio of the copper oxide to the manganese oxide is 20: 70: 3, the other metal oxide is a mixture of praseodymium oxide, samarium oxide, europium oxide, gadolinium oxide, potassium oxide and calcium oxide;
2) adding water with the mass 1.5 times of that of the mixture into the pug, uniformly mixing, transferring the mixture into a kneader, and stirring for 60min at 36 revolutions per minute to uniformly mix the pug;
3) and tightly packaging the pug with a preservative film, and aging for 24 hours under the conditions that the environmental temperature is 20 ℃ and the environmental humidity is 90%.
4) Putting the aged pug into a bar extruder to be pressed to generate a honeycomb-shaped formed catalyst; the extrusion pressure was 20 MPa.
5) And (5) five-stage drying: firstly, drying at 15 ℃, drying in a constant-temperature constant-humidity box with the humidity of 90% until the moisture content is less than 40 wt%, slowly heating the embryo body to 30 ℃ for drying, drying until the moisture content is less than 30 wt%, slowly heating the embryo body to 40 ℃ for drying, drying until the moisture content is less than 20 wt%, slowly heating the embryo body to 50 ℃ for drying, drying until the moisture content is less than 10 wt%, and slowly heating the embryo body to 100 ℃ until the embryo body is completely dried; the catalyst is turned over at regular time in the drying process to ensure that the integrity of the catalyst is good.
6) Three-stage roasting: heating to 200 deg.C at 1 deg.C/min from room temperature, calcining for 4h, heating to 400 deg.C at 0.8 deg.C/min for 10h, heating to 500 deg.C at 8 deg.C/min for 9h, and cooling to room temperature.
Comparative example 1
The specific procedure was identical to example 1 except that the drying process was one stage drying: drying is carried out in a constant temperature and humidity box, the humidity is 40%, the temperature is raised to 110 ℃ until the drying is complete, and the catalyst is turned over at regular time in the drying process to ensure that the integrity of the catalyst is good.
Comparative example 2
The specific operation steps are the same as those in example 1, except that the roasting process is one-stage roasting: heating from room temperature to 400 deg.C at 0.5 deg.C/min, calcining for 12 hr, and cooling to room temperature.
Comparative example 3
The procedure was as in example 1 except that the humidity was 20% during the drying process.
Comparative example 4
The procedure was as in example 1 except that the humidity was 10% during the drying process.
Comparative example 5
The specific procedure was the same as in example 1 except that the drying process was carried out in a completely dry environment without maintaining a certain humidity.
Example 4
The specific operation steps are the same as those in example 1, except that the mass ratio of the effective components of the catalyst powder, namely copper oxide, manganese oxide and other metal oxides is 20: 70: 5.
example 5
The specific operation steps are the same as those in example 1, except that the mass ratio of the effective components of the catalyst powder, namely copper oxide, manganese oxide and other metal oxides is 20: 70: 7.
experimental example 1
The catalyst effects of examples 1 to 3 and comparative examples 1 to 8 were evaluated, and the specific experimental evaluation methods were as follows:
the sintered flue gas was passed through the prepared honeycomb catalyst (dimensions 50mm x 50mm), the initial CO concentration: 7900ppm, other gas components: 20% O2，8％H2O，5CO2，N2It is the balance gas. The flue gas flow is 25m3The space velocity is 200000h-1The CO concentration before and after the flow was measured. CO removal rate (inlet gas concentration-outlet gas concentration)/(inlet gas concentration).
The catalyst has the stability, and is prepared by ultrasonic treatment in a JP-020PLUS ultrasonic cleaning machine with 180W power (ultrasonic frequency of 40KHz) for 10min/30min/60min, drying and weighing. The exfoliation rate is (mass before treatment-mass after treatment)/mass before treatment.
The catalyst was weighed 72 hours after the catalyst was used, and the shedding rate after 72 hours (mass before use-mass after use)/mass before use.
Compressive strength: two test blocks of 50mm × 50mm × 50mm under each preparation condition were cut out, respectively, and the axial and transverse compressive strengths were measured with a compression tester.
TABLE 1 evaluation results of catalyst Effect
Figure BDA0002806589960000131
From the comparative data of the embodiment 1 and the embodiments 4 to 5, it can be seen that the effective components of the catalyst of the present invention, in addition to manganese oxide and copper oxide, are additionally added with other metal oxides, but the quality of the other metal oxides needs to be controlled within a relatively proper range, because the addition of these metals improves the catalytic effect of the catalyst to a certain extent, and also improves the water resistance of the catalyst itself.
From the comparative data of the example 1 and the comparative examples 1-2, it can be seen that the catalytic performance and the catalyst stability are influenced when the catalyst is in a single-stage roasting state or a single-stage drying state, so that the invention finds a specially adopted mode of drying for multiple times and roasting for multiple times through practice.
As can be seen from the comparative data of example 1 and comparative examples 3-5, the drying process needs to be performed under the conditions of constant humidity and proper humidity, otherwise, the completely dried state is very unfavorable for the stability of the catalyst itself.
In addition, it can be seen from the catalytic efficiency curve of fig. 1 that the honeycomb formed catalyst of the present invention exhibits superior catalytic performance at lower temperatures, and similar results are obtained by performing corresponding experiments on the catalysts of other examples.
In summary, the honeycomb shaped catalyst prepared by the above method has the following effects:
the honeycomb catalyst has good water resistance, and can have high CO catalytic efficiency in flue gas containing 1-20% of water.
② the honeycomb catalyst can be used at the space velocity of 200000h-1And the concentration of CO in the steel sintering flue gas is reduced to less than or equal to 1000ppm under the low-temperature condition of 130 ℃.
The honeycomb catalyst has good stability, and can ensure that the removal rate of CO in the sintering flue gas is more than or equal to 90 percent when the honeycomb catalyst is continuously used for 72 hours in the using process.
The honeycomb catalyst has good stability, and can be continuously used for 72 hours in the using process, and the falling rate of the catalyst powder is less than or equal to 1 percent.
The honeycomb catalyst has good compressive strength. The compression strength is that two test blocks with the thickness of 50mm multiplied by 50mm are respectively cut out, and the axial compression strength and the transverse compression strength are tested by a compression testing machine.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (10)

1. The honeycomb forming catalyst is characterized by being prepared by mainly using manganese oxide and copper oxide as main components and using other metal oxides as auxiliary components; wherein the mass ratio of the copper oxide to the manganese oxide to the other metal oxides is (5-50): (50-90): (1-10).
2. A honeycomb shaped catalyst as claimed in claim 1 wherein the other metal oxides include any one or more of cerium oxide, tin oxide, cobalt oxide, lanthanum oxide, praseodymium oxide, samarium oxide, europium oxide, gadolinium oxide, potassium oxide, calcium oxide, zinc oxide, magnesium oxide and nickel oxide.
3. The method of making a honeycomb shaped catalyst according to any one of claims 1 to 2, comprising the steps of:
mixing the catalyst raw powder with a binder, a peptizing agent, an extrusion aid, a pore-forming agent and a forming aid to form a mixture;
adding water into the mixture, uniformly mixing, kneading, aging, extruding, molding, drying and roasting in sequence;
the drying is sectional drying, each section of drying keeps constant temperature and humidity, the humidity is kept at 50-90%, and the roasting is sectional roasting.
4. The preparation method according to claim 3, wherein the number of stages of the drying process is 2-10, the drying temperature of the 1 st stage is 15-20 ℃, the temperature of each subsequent stage is 10-15 ℃ higher, and the drying temperature of the last stage is 100-110 ℃.
5. The preparation method according to claim 3, wherein the number of stages in the roasting process is 2-4, the temperature rise rate of each roasting stage of the first 1-3 stages is controlled to be 0.5-2 ℃/min, the temperature is controlled to be 100-300 ℃, the roasting time is 2-12 h, the temperature rise rate of the last stage is controlled to be 2-10 ℃/min, the temperature is controlled to be 400-700 ℃, and the roasting time is 2-12 h.
6. The preparation method according to claim 3, wherein the binder is 10 to 50 wt% of the mixture;
the binder is any one or more of marble glue, AB glue, starch, polyvinyl alcohol, kaolin, hydrotalcite, silica sol, sodium silicate, alumina sol, polyacrylamide, methyl cellulose, sodium carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, corn oil, carboxypropyl methyl cellulose, tall oil, sodium stearate, starch, aluminum dihydrogen phosphate solution, aluminosilicate, pseudo-boehmite, mullite fiber, spodumene, eucryptite, ammonium methyl cellulose, asphalt, coal tar and cellulose.
7. The preparation method according to claim 3, wherein the peptizing agent accounts for 1-15 wt% of the mixture;
the type of the peptizing agent is any one or more of nitric acid, hydrochloric acid, acetic acid, formic acid, citric acid, trichloroacetic acid and malonic acid;
preferably, the extrusion aid is 1-15 wt% of the mass of the mixture;
the type of the extrusion aid is any one or more of sesbania powder, glycerol, salad oil, oxalic acid, tartaric acid, citric acid, polyacrylamide, stearic acid, glycerol, corn oil, tall oil, sodium stearate, palm oil, soybean oil, castor oil and acetic acid.
8. The preparation method according to claim 3, wherein the pore-forming agent is 1 to 10 wt% of the mixture;
the pore-forming agent is any one or more of activated carbon, wood chips, kapok, starch, polyethylene glycol, urea, cellulose, polyoxyethylene, sesbania powder and sponge.
9. The preparation method according to claim 3, wherein the forming aid is 0.1-5 wt% of the mixture;
the forming auxiliary agent comprises any one or more of glass fiber, pulp fiber, lactic acid and ethanolamine.
10. Use of the honeycomb shaped catalyst according to any one of claims 1 to 2 and the honeycomb shaped catalyst prepared by the preparation method according to any one of claims 3 to 9 for catalytic oxidation of CO in the field of sintered flue gas.
CN202011372709.6A 2020-11-30 2020-11-30 Honeycomb body forming catalyst and preparation method and application thereof Pending CN114570434A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011372709.6A CN114570434A (en) 2020-11-30 2020-11-30 Honeycomb body forming catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011372709.6A CN114570434A (en) 2020-11-30 2020-11-30 Honeycomb body forming catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114570434A true CN114570434A (en) 2022-06-03

Family

ID=81767254

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011372709.6A Pending CN114570434A (en) 2020-11-30 2020-11-30 Honeycomb body forming catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114570434A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155607A (en) * 2022-07-12 2022-10-11 中晶环境科技股份有限公司 Solid catalyst, process for producing the same and use thereof
CN117839773A (en) * 2024-03-04 2024-04-09 北京科技大学 Monolithic carbon monoxide catalyst and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104162440A (en) * 2014-08-04 2014-11-26 南昌大学 Preparation method for high-water-resistance copper, manganese and tin composite oxide CO low-temperature oxidization catalyst
CN104815644A (en) * 2015-03-16 2015-08-05 南通亚泰工程技术有限公司 Porous honeycomb type denitration catalyst for ship denitration, preparation method and application thereof
CN105126818A (en) * 2015-08-28 2015-12-09 湖北省轻工业科学研究设计院 Wear-resistant anti-poisoning honeycomb SCR denitration catalyst and preparation method thereof
CN107537515A (en) * 2017-09-11 2018-01-05 中国科学技术大学 A kind of application of carried copper Mn catalyst and preparation method thereof and CO catalytic oxidation under low temperature
CN108126688A (en) * 2017-12-05 2018-06-08 华南理工大学 A kind of Faveolate denitration catalyst and preparation method thereof
CN108144601A (en) * 2018-02-05 2018-06-12 安徽弘昇环境工程科技有限公司 SCR (Selective catalytic reduction) ultralow-temperature denitration catalyst and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104162440A (en) * 2014-08-04 2014-11-26 南昌大学 Preparation method for high-water-resistance copper, manganese and tin composite oxide CO low-temperature oxidization catalyst
CN104815644A (en) * 2015-03-16 2015-08-05 南通亚泰工程技术有限公司 Porous honeycomb type denitration catalyst for ship denitration, preparation method and application thereof
CN105126818A (en) * 2015-08-28 2015-12-09 湖北省轻工业科学研究设计院 Wear-resistant anti-poisoning honeycomb SCR denitration catalyst and preparation method thereof
CN107537515A (en) * 2017-09-11 2018-01-05 中国科学技术大学 A kind of application of carried copper Mn catalyst and preparation method thereof and CO catalytic oxidation under low temperature
CN108126688A (en) * 2017-12-05 2018-06-08 华南理工大学 A kind of Faveolate denitration catalyst and preparation method thereof
CN108144601A (en) * 2018-02-05 2018-06-12 安徽弘昇环境工程科技有限公司 SCR (Selective catalytic reduction) ultralow-temperature denitration catalyst and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
吴志杰: "《能源转化催化原理》", 31 July 2018, 中国石油大学出版社, pages: 184 - 185 *
唐婕等编著: "《环保陶瓷生产与应用》", 31 January 2018, 中国建材工业出版社, pages: 208 *
朱崇兵;金保升;仲兆平;李锋;翟俊霞;: "蜂窝状催化剂的制备及其性能评价", 动力工程, no. 03, pages 459 - 464 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155607A (en) * 2022-07-12 2022-10-11 中晶环境科技股份有限公司 Solid catalyst, process for producing the same and use thereof
CN115155607B (en) * 2022-07-12 2024-05-28 中晶环境科技股份有限公司 Solid catalyst, method for producing the same and use thereof
CN117839773A (en) * 2024-03-04 2024-04-09 北京科技大学 Monolithic carbon monoxide catalyst and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN114570435A (en) Honeycomb catalyst and preparation method and application thereof
CN114570434A (en) Honeycomb body forming catalyst and preparation method and application thereof
CN108067296B (en) A kind of preparation method of honeycomb Mn based low-temperature denitration catalyst
CN106000455B (en) A kind of environmental-friendly SCR catalyst and preparation method thereof
CN102413905B (en) Ceria-zirconia-zeolite catalyst body
CN113117727B (en) Preparation method of honeycomb ceramic catalyst for catalytic oxidation of flue gas CO
CN104475122A (en) Forming SCR catalyst with both water resistance and sulphur resistance and preparation method thereof
CN113426438B (en) Coated catalyst composition, catalytic filter tube and preparation method thereof
CN105618077B (en) A kind of preparation method of denitration honeycomb ceramic catalyst and its catalyst of preparation
CN103933971A (en) Low-temperature denitration catalyst as well as preparation method and application thereof
CN101905145B (en) Molecular sieve cellular material and preparation method thereof
CN106140150A (en) A kind of honeycomb fashion cerium zirconium manganese titanio denitrating catalyst and preparation method thereof
CN107008323B (en) A kind of activated-carbon catalyst preparation method for flue gas desulfurization and denitrification
CN110694612A (en) Rare earth-based low-vanadium medium-low temperature flue gas denitration catalyst and preparation method thereof
CN113351155A (en) Adsorbing material and preparation method and application thereof
CN109745966A (en) Environment-friendly catalyst for SCR denitration and preparation method thereof
CN114260015A (en) Flue gas denitration molded catalyst and preparation method and application thereof
CN115364868B (en) Catalyst for catalytically decomposing ozone and preparation method thereof
CN109967069A (en) A kind of low-temperature SCR catalyst and preparation method thereof for cement kiln flue gas denitration
CN114602490A (en) Preparation method of integral catalytic combustion CO catalyst
CN107335423A (en) A kind of honeycomb fashion is without vanadium cerium zirconium titanium denitrating catalyst and preparation method thereof
CN101716535B (en) Method for preparing waste gas purifying catalyst
CN112717967A (en) Rare earth-based medium-low temperature SCR catalyst and preparation method thereof
CN110694640A (en) Water-resistant sulfur-resistant denitration catalyst and preparation method thereof
CN106881148B (en) A kind of cellular wide temperature denitrating catalyst and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20221115

Address after: 523722 Room 907, Building 8, No. 95, Jiaoping Road, Tangxia Town, Dongguan City, Guangdong Province

Applicant after: Zhongke Huizhi (Dongguan) Equipment Technology Co.,Ltd.

Address before: Room 6059, building 2, China Agricultural University International Business Park, 10 Tianxiu Road, Haidian District, Beijing, 100193

Applicant before: Zhongda huizhiyuanchuang (Beijing) Technology Co.,Ltd.

TA01 Transfer of patent application right