CN111744494B - Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof - Google Patents

Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof Download PDF

Info

Publication number
CN111744494B
CN111744494B CN202010527741.0A CN202010527741A CN111744494B CN 111744494 B CN111744494 B CN 111744494B CN 202010527741 A CN202010527741 A CN 202010527741A CN 111744494 B CN111744494 B CN 111744494B
Authority
CN
China
Prior art keywords
catalyst
solution
flat
prepared
gamma
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.)
Active
Application number
CN202010527741.0A
Other languages
Chinese (zh)
Other versions
CN111744494A (en
Inventor
曲艳超
陈晨
陆强
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.)
Beijing Huadian Guangda Environment Co ltd
Original Assignee
Beijing Huadian Guangda Environment 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 Beijing Huadian Guangda Environment Co ltd filed Critical Beijing Huadian Guangda Environment Co ltd
Priority to CN202010527741.0A priority Critical patent/CN111744494B/en
Publication of CN111744494A publication Critical patent/CN111744494A/en
Application granted granted Critical
Publication of CN111744494B publication Critical patent/CN111744494B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • 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
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • 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
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
    • B01D53/8646—Simultaneous elimination of the components
    • B01D53/865—Simultaneous elimination of the components characterised by a specific catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • B01J37/20—Sulfiding
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (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 embodiment of the invention provides a flat-plate type CO and SO 2 And NO x A synchronous removal catalyst and a preparation method thereof. The catalyst carrier is gamma-Al 2 O 3 Nanotube with La as active component 0.8 Sr 0.2 Co x Mo 1‑ x O 3 And perovskite, a flat plate type catalyst is prepared by adopting a roll coating process, and the final catalyst is prepared by pre-vulcanizing before the catalyst is used. The catalyst is prepared from gamma-Al 2 O 3 The nano tube is used as a carrier, so that the uniform distribution of active components is facilitated, the specific surface area of the catalyst can be greatly increased, and the catalyst has good catalytic activity and anti-poisoning performance within the range of 300-450 ℃; la 0.8 Sr 0.2 Co x Mo 1‑x O 3 The perovskite structure can realize CO and SO 2 And NO x Synchronously removing the three pollutants; the catalyst is pre-vulcanized to reduce SO to CO 2 Has good catalytic activity and contains O 2 And H 2 The real smoke of O has good reaction activity and selectivity; and by adding the forming auxiliary agent, the preparation process is optimized, the prepared catalyst has the advantages of reduced pressure, long service life, reduced investment and operation cost, and good economic benefit.

Description

Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of environmental protection and denitration catalysis, and particularly relates to a flat plate type CO and SO 2 And NO x The catalyst is synchronously removed, and the synchronous removal of CO, nitrogen and sulfur pollutants can be realized. The invention also provides the flat-plate type CO and SO 2 And NO x A preparation method of synchronously removing a catalyst.
Background
Sulfur dioxide (SO) 2 ) And Nitrogen Oxides (NO) x ) Is an important atmospheric pollutant, can cause acid rain, photochemical smog, ozone layer damage and the like, and causes great harm to the environment and human health. Coal is one of the most important energy sources in China, namely SO discharged by coal-fired power plants 2 And NO x Accounting for more than 90% of the total discharge. At present, coal-fired power plants are widely usedThe desulfurization process that floodly adopts is limestone gypsum wet Flue Gas Desulfurization (FGD), and denitration process is Selective Catalytic Reduction (SCR), and two sets of independent devices all have desulfurization efficiency and denitration efficiency than ideal, nevertheless if use two sets of devices to carry out joint desulfurization denitration, then have area big, and the system is complicated, shortcomings such as investment and running cost height.
The flue gas usually contains a certain amount of carbon monoxide (CO), SO the CO existing in the flue gas is used as a reducing agent to reduce SO 2 And NO x Reduction to elemental sulfur and N 2 Not only can realize CO and SO 2 And NO x The method has the advantages of synchronous removal of the three pollutants, no need of adding an additional reducing agent, simple process, low operation cost and wide application prospect. But CO reduces SO 2 And NO x The reaction of (a) needs to be carried out in the presence of a catalyst, and therefore, the development of a catalyst with high activity, selectivity and stability is the core of the process. Chinese patent document CN102049257A discloses CO simultaneous reduction SO 2 And NO as catalyst, in TiO 2 -Al 2 O 3 The composite oxide is used as carrier, the transition metal oxide is used as active component, after said catalyst is presulfurized, under the condition of low temp. and high air speed 98% SO can be obtained 2 Conversion and near 100% NO conversion, but the remaining CO in the flue gas is not further treated and is still vented to the atmosphere. Chinese patent document CN103464154A also discloses a method for simultaneously catalyzing and reducing NO and SO by CO 2 The catalyst of (1), the catalyst being prepared from gamma-Al 2 O 3 Is a carrier and is loaded with metal oxide. The catalyst can effectively reduce SO 2 And NO, but the residual CO can not be removed, so that the CO emission of the tail gas exceeds the standard. In view of the above technical problems of the existing catalysts, the development of a catalyst capable of realizing CO and SO is urgently needed 2 And NO x High efficiency and synchronous removal of catalyst.
Disclosure of Invention
The invention provides a flat plate type CO and SO for solving the technical problem that residual CO cannot be synchronously treated in the existing synchronous desulfurization and denitrification process 2 And NO x Synchronous removal of catalyst anda process for its preparation, said catalyst reducing SO to CO 2 And NO x The reaction has high activity and can oxidize CO into CO 2 Also has high activity, and can efficiently realize CO and SO 2 And NO x The synchronization is removed.
To solve the above technical problems, embodiments of the present invention provide a flat plate type CO and SO 2 And NO x The catalyst is a flat structure and comprises 5-20% of La by mass 0.8 Sr 0.2 Co x Mo 1-x O 3 And 80 to 95% of gamma-Al 2 O 3 Nanotubes, said catalyst having been presulfided.
Preferably, the La 0.8 Sr 0.2 Co x Mo 1-x O 3 Is perovskite structure, wherein x is 0.5-0.7.
Preferably, the gamma-Al 2 O 3 The length of the nano tube is 250-300 nm, and the outer diameter is 18-20 nm.
The embodiment of the invention also provides the flat-plate type CO and SO 2 And NO x The preparation method of the synchronous removal catalyst comprises the following steps:
step 1, catalyst carrier preparation, namely, under the condition of stirring, adding AlCl 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; adding hydrogen peroxide solution into hexadecyl trimethyl ammonium bromide solution at 45 ℃, stirring uniformly, and then adding NaAlO 2 Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, then carrying out reaction at 120 ℃ for 12h, washing and filtering the product, drying the product in the air at 80-120 ℃ for 12-24 h, and roasting the product in the air at 500-550 ℃ for 4-24 h to prepare the gamma-Al 2 O 3 A nanotube;
step 2, catalyst mud preparation, namely according to La 0.8 Sr 0.2 Co x Mo 1-x O 3 The amount of lanthanum, strontium, cobalt and molybdenum is respectively proportional to the amount of nitrateSequentially adding lanthanum nitrate, strontium nitrate, cobalt nitrate and ammonium heptamolybdate into deionized water, adding citric acid after completely dissolving, and stirring for 1-2 h at 40-60 ℃; adding the obtained solution into the gamma-Al prepared in the step 1 2 O 3 Adding montmorillonite, glass fiber, polyethylene oxide and carboxymethyl cellulose into the nano tube, stirring uniformly, and aging for 24-48 h under a closed condition to prepare catalyst mud;
and 3, preparing a flat-plate catalyst, comprising the following steps:
step 31, forming the flat-plate catalyst, namely extruding the catalyst mud material prepared in the step 2 by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, creasing and shearing the stainless steel screen plate, drying the stainless steel screen plate for 5 to 10min at 105 to 120 ℃ in the air, and roasting the dried catalyst mud material for 4 to 8h at 750 to 800 ℃ in the air to prepare the flat-plate catalyst;
step 32, presulfurizing the catalyst, namely, the flat-plate catalyst prepared in the step 31 is prepared by CO and SO 2 、O 2 And N 2 Treating the pre-vulcanized gas at 200 ℃ for 1-4 h; then cut off SO 2 Heating the gas to 300-400 ℃ and keeping the temperature for 1-4 h; finally heating to 600-700 ℃ and introducing SO 2 Keeping the gas for 2 to 6 hours to prepare the prevulcanized flat plate type La 0.8 Sr 0.2 Co x Mo 1-x O 3 /γ-Al 2 O 3 The catalyst is the flat-plate type CO or SO 2 And NO x And synchronously removing the catalyst.
Preferably, in step 1, the AlCl is 3 The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl 3 And NaOH in a molar ratio of 1.
As the optimization of the step 1, the concentration of the hexadecyl trimethyl ammonium bromide solution is 0.3mol/L.
As a preference of step 2, the amount of the substance of citric acid added to the deionized water is equal to the total amount of the metal ion substance added.
Preferably, in step 2, the glass fiber has a length of 4 to 6mm.
Preferably, in step 2, the polyacrylamide is anionic and has a molecular weight of 200 to 400 ten thousand.
Preferably, in step 32, CO and SO in the pre-sulfiding gas 2 、O 2 And N 2 The volume ratio of each component is respectively 10%, 2%, 5% and 83%.
The technical scheme of the embodiment of the invention provides a novel gamma-Al 2 O 3 Nanotube as carrier, la 0.8 Sr 0.2 Co x Mo 1-x O 3 Perovskite is an active component, and the catalyst can synchronously remove CO and SO in flue gas through presulfurizing the treated catalyst 2 And NO x The beneficial effects are as follows:
1.γ-Al 2 O 3 the nanotube is used as a carrier, so that the uniform distribution of active components is facilitated, the specific surface area of the catalyst can be greatly increased, and the activity of the catalyst is effectively improved; meanwhile, gamma-Al is properly selected 2 O 3 The length and the outer diameter of the nanotube can ensure that the nanotube has larger specific surface area as a carrier and does not reduce the mechanical strength of the catalyst; thirdly, gamma-Al 2 O 3 The unique tubular cavity structure of the nanotube can lead most active components to be fixed inside the pipeline, and the gamma-Al 2 O 3 The nanotube pipeline can effectively isolate solid toxic substances such as alkali metal, heavy metal and the like outside the pipeline, thereby avoiding the inactivation of active components due to the influence of the toxic substances in the flue gas and improving the anti-poisoning performance of the catalyst;
2.La 0.8 Sr 0.2 Co x Mo 1-x O 3 perovskite structure to SO 2 And NO x Has good reducibility and selectivity, simultaneously has good catalytic oxidation performance on CO, and can convert SO 2 Reduction to elemental sulfur, NOx to N 2 Oxidation of CO to CO 2 The synchronous removal of the three pollutants is realized;
3. after the catalyst is subjected to pre-vulcanization treatment, the metal-sulfur bond in the Co-Mo-S structure can also reduce SO to CO 2 Has good catalytic activity; and part of La is generated after prevulcanization 2 O 2 S, theThe substance has double active centers, not only has the active center which reacts with CO to form intermediate product COS, but also promotes COS and SO 2 The active center of the reaction is adopted, no COS is generated in the product, and the selectivity of the reaction is very high;
4. the catalyst is pre-sulfurized and then contains O 2 And H 2 The real smoke of O has good reaction activity and selectivity, and the catalyst has excellent anti-oxidation poisoning performance;
5. by adding various inorganic and organic forming aids, the preparation process is optimized, the flat-plate catalyst with high mechanical property is prepared, the pressure drop is low, the service life is long, the investment and the operation cost are reduced, and the economic benefit is good.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
Aiming at the existing problems, the invention provides a flat-plate type CO and SO 2 And NO x Synchronous removal of catalyst, which can efficiently realize CO and SO 2 And NO x The synchronization is removed.
In order to realize the technical scheme, the embodiment of the invention provides a flat-plate type CO and SO 2 And NO x The catalyst is a flat structure and comprises 5-20 wt% of La 0.8 Sr 0.2 Co x Mo 1-x O 3 And 80 to 95% of gamma-Al 2 O 3 Nanotubes and catalyst are presulfurized. As a more preferred embodiment, la 0.8 Sr 0.2 Co x Mo 1- x O 3 Is of a perovskite structure, wherein x is 0.5 to 0.7; gamma-Al 2 O 3 The length of the nano tube can be selectively controlled to be 250-300 nm, the external diameter size is controlled to be 18-20 nm, and the gamma-Al can be ensured 2 O 3 The nanotube as catalyst carrier has relatively great specific surface area and no lowering of the mechanical strength of the catalyst.
In order to better realize the technical scheme, the invention also provides the flatPlate type CO and SO 2 And NO x The preparation method of the synchronous removal catalyst comprises the following steps:
s1, preparing a catalyst carrier, namely, under the stirring condition, adding AlCl 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; adding hydrogen peroxide solution into hexadecyl trimethyl ammonium bromide solution at 45 ℃, stirring uniformly, and then adding NaAlO 2 Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, then carrying out reaction at 120 ℃ for 12h, washing and filtering the product, drying the product in the air at 80-120 ℃ for 12-24 h, and roasting the product in the air at 500-550 ℃ for 4-24 h to obtain the gamma-Al 2 O 3 A nanotube;
s2, preparing catalyst mud, namely preparing catalyst mud according to La 0.8 Sr 0.2 Co x Mo 1-x O 3 Lanthanum nitrate, strontium nitrate, cobalt nitrate and ammonium heptamolybdate are added into deionized water in turn according to the proportion of the amount of lanthanum, strontium, cobalt and molybdenum elements, citric acid is added after complete dissolution, and stirring is carried out for 1-2 h at 40-60 ℃; adding the obtained solution into the gamma-Al prepared in the step 1 2 O 3 Adding montmorillonite, glass fiber, polyethylene oxide and carboxymethyl cellulose into the nanotube and stirring uniformly, and aging for 24-48 h under a closed condition to prepare catalyst mud;
s3, preparing a flat-plate catalyst, comprising the following steps:
s31, forming a flat-plate catalyst, namely extruding the catalyst mud prepared in the step S2 by an extruder, placing the extruded catalyst mud on a stainless steel screen plate, rolling, coating, pleating and shearing the stainless steel screen plate, drying the stainless steel screen plate in the air at 105-120 ℃ for 5-10 min, and roasting the dried catalyst mud in the air at 750-800 ℃ for 4-8 h to prepare the flat-plate catalyst;
s32, presulfurizing the catalyst, namely, preparing the flat-plate catalyst prepared in the step S31 from CO and SO 2 、 O 2 And N 2 Treating the pre-vulcanized gas at 200 ℃ for 1-4 h; then cut off SO 2 Gas is heated toKeeping the temperature at 300-400 ℃ for 1-4 h; finally heating to 600-700 ℃ and introducing SO 2 Keeping the gas for 2 to 6 hours to prepare the prevulcanized flat plate type La 0.8 Sr 0.2 Co x Mo 1-x O 3 /γ-Al 2 O 3 The catalyst is the flat-plate type CO or SO 2 And NO x And synchronously removing the catalyst.
As a more preferred embodiment:
in step S1, alCl 3 The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl 3 And NaOH in a molar ratio of 1; the concentration of the hexadecyl trimethyl ammonium bromide solution is 0.3mol/L;
in the step S2, the amount of the citric acid substances added into the deionized water is equal to the total amount of the added metal ion substances; the length of the glass fiber is 4-6 mm; the polyacrylamide is anionic and has molecular weight of 200-400 ten thousand.
In step S32, CO and SO in the presulfurized gas 2 、O 2 And N 2 The volume ratio of each component is respectively 10%, 2%, 5% and 83%.
The technical scheme of the invention is specifically described by the following specific embodiments:
example 1
Flat plate type CO and SO 2 And NO x The preparation method comprises the following specific steps:
(1)γ-Al 2 O 3 nanotube support preparation
Respectively dissolving 6.544kg of AlCl in 98L of deionized water 3 24.5L of deionized water is used for dissolving 3.922kg of NaOH, and then the prepared AlCl is stirred 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 40 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO 2 Stirring the solution evenly, and adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, and then carrying out reaction at 120 ℃ for 12h; washing the obtained product with water, filteringDrying in air at 80 deg.C for 24 hr, calcining in air at 500 deg.C for 24 hr, and collecting 2417g of gamma-Al 2 O 3 A nanotube support.
(2) Preparation of catalyst mud
131.98g of La (NO) was weighed out 3 ) 3 6H 2 O, 16.13g of Sr (NO) 3 ) 2 56.55g of Co (NO) 3 ) 2 6H 2 O and 32.94g of (NH) 4 ) 6 Mo 7 O 24 Dissolving in 1.24L water, adding 146.4g citric acid, and stirring at 40 deg.C for 1 hr; the prepared solution was added to 1900g of gamma-Al 2 O 3 And adding montmorillonite, 4mm glass fiber, polyethylene oxide and carboxymethyl cellulose into the carrier, and aging for 24 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Extruding the obtained catalyst mud material with extruder, placing on stainless steel mesh plate, roll-coating, crimping, shearing, drying in air at 105 deg.C for 5min, and calcining in air at 750 deg.C for 4h to obtain 5% La 0.8 Sr 0.2 Co 0.51 Mo 0.49 O 3 /95％γ-Al 2 O 3 A flat catalyst with the components in percentage by mass;
the prepared flat-plate catalyst is prepared by mixing 10 volume percent of CO and 2 volume percent of SO 2 5% of O 2 And 83% of N 2 Treating the mixture for 1h at 200 ℃ in the formed prevulcanization gas; then cutting off SO 2 Heating the gas to 300 ℃, and keeping the temperature for 1h; finally heating to 600 ℃, and introducing SO 2 Keeping the gas for 2h to obtain the presulfurized flat catalyst.
The prepared catalyst component is 5 percent by mass of La 0.8 Sr 0.2 Co 0.51 Mo 0.49 O 3 /95％γ-Al 2 O 3 。
Example 2
Another flat plate type CO and SO 2 And NO x The preparation method comprises the following specific steps:
(1)γ-Al 2 O 3 nanotube support preparation
7.853kg of AlCl were dissolved in 117.6L of deionized water, respectively 3 29.4L of deionized water was dissolved in 4.706kg of NaOH, and then the prepared AlCl was stirred 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 40 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO 2 Stirring the solution evenly, and adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, and then carrying out reaction at 120 ℃ for 12h; washing the obtained product with water, filtering, drying in air at 120 deg.C for 12h, calcining in air at 550 deg.C for 4h, and collecting 2897g of gamma-Al 2 O 3 A nanotube support.
(2) Preparation of catalyst mud
827.90g of La (NO) was taken 3 ) 3 6H 2 O, 101.16g of Sr (NO) 3 ) 2 479.93g of Co (NO) 3 ) 2 6H 2 O and 130.72g of (NH) 4 ) 6 Mo 7 O 24 Dissolving in 1.85L water, adding 918.38g citric acid, and stirring at 60 deg.C for 2h; 2400g of gamma-Al were added to the prepared solution 2 O 3 And adding montmorillonite, 6mm glass fiber, polyethylene oxide and carboxymethyl cellulose into the carrier, and aging for 48 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Extruding the obtained catalyst mud material by an extruder, placing on a stainless steel screen plate, rolling, coating, pleating, shearing, drying in air at 120 deg.C for 10min, and calcining in air at 800 deg.C for 8h to obtain 20% La 0.8 Sr 0.2 Co 0.69 Mo 0.31 O 3 /80％γ-Al 2 O 3 A flat catalyst with the components in percentage by mass;
the prepared flat-plate catalyst is prepared by mixing 10 volume percent of CO and 2 volume percent of SO 2 5% of O 2 And 83% of N 2 Treating the pre-vulcanized gas for 4 hours at 200 ℃; however, the device is not limited to the specific type of the devicePost-cut off SO 2 Heating the gas to 400 ℃, and keeping the temperature for 4 hours; finally heating to 700 ℃, and introducing SO 2 Keeping the gas for 6h to obtain the presulfurized flat catalyst.
The obtained catalyst component is 20% by mass of La 0.8 Sr 0.2 Co 0.69 Mo 0.31 O 3 /80％γ-Al 2 O 3 。
Example 3
Another flat plate type CO and SO 2 And NO x The preparation method comprises the following specific steps:
(1)γ-Al 2 O 3 nanotube support preparation
9.162kg of AlCl are dissolved in 137.3L of deionized water respectively 3 34.3L of deionized water was dissolved in 5.490kg of NaOH, and then the prepared AlCl was stirred 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 40 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO 2 Stirring the solution evenly, and adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, and then carrying out reaction at 120 ℃ for 12h; washing the obtained product with water, filtering, drying in air at 110 deg.C for 15h, calcining in air at 525 deg.C for 5h, and collecting 3421g of gamma-Al 2 O 3 A nanotube support.
(2) Preparation of catalyst mud
404.60g of La (NO) was taken 3 ) 3 6H 2 O, 49.44g Sr (NO) 3 ) 2 203.95g of Co (NO) 3 ) 2 6H 2 O and 82.43g of (NH) 4 ) 6 Mo 7 O 24 Dissolving in 2.15L water, adding 448.82g citric acid, and stirring at 50 deg.C for 1.5 hr; the prepared solution was added with 2700g of gamma-Al 2 O 3 And adding montmorillonite, 5mm glass fiber, polyethylene oxide and carboxymethyl cellulose into the carrier, and aging for 36h under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Extruding the obtained catalyst mud material by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, creasing and shearing, drying at 110 ℃ for 7min in air, and roasting at 800 ℃ for 4h in air to obtain the 10% La 0.8 Sr 0.2 Co 0.6 Mo 0.4 O 3 /90％γ-Al 2 O 3 A flat catalyst with the components in percentage by mass;
the prepared flat-plate catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO 2 5% of O 2 And 83% of N 2 Treating the mixture in pre-sulfuration gas at 200 ℃ for 2.5 hours; then cutting off SO 2 Heating the gas to 400 ℃, and keeping the temperature for 1.5h; finally, the temperature is raised to 650 ℃, and SO is introduced 2 Keeping the gas for 4.5 hours to obtain the presulfurized flat catalyst.
The obtained catalyst component is La by mass percentage of 10% 0.8 Sr 0.2 Co 0.6 Mo 0.4 O 3 /90％γ-Al 2 O 3 。
Example 4
Another flat plate type CO and SO 2 And NO x The preparation method comprises the following specific steps:
(1)γ-Al 2 O 3 nanotube support preparation
Respectively dissolving 10.471kg of AlCl in 156.9L of deionized water 3 39.2L of deionized water was dissolved in 6.274kg of NaOH and the prepared AlCl was stirred 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; heating 0.3mol/L hexadecyl trimethyl ammonium bromide solution to 40 ℃, adding a proper amount of hydrogen peroxide solution, and slowly dropwise adding NaAlO 2 Stirring the solution evenly, and adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, and then carrying out reaction at 120 ℃ for 12h; washing the obtained product with water, filtering, drying in air at 105 deg.C for 18h, calcining in air at 520 deg.C for 6.5h, and collecting 3917g of gamma-Al 2 O 3 A nanotube support.
(2) Preparation of catalyst mud
803.30g of La (NO) was taken 3 ) 3 6H 2 O, 98.15g of Sr (NO) 3 ) 2 384.69g of Co (NO) 3 ) 2 6H 2 O and 175.93g of (NH) 4 ) 6 Mo 7 O 24 Dissolving in 2.85L water, adding 891.10g citric acid, and stirring at 55 deg.C for 1.5h; 3400g of gamma-Al is added to the prepared solution 2 O 3 And adding montmorillonite, 4mm glass fiber, polyethylene oxide and carboxymethyl cellulose into the carrier, and aging for 30 hours under a closed condition to obtain the catalyst mud.
(3) Catalyst shaping and presulfiding
Extruding the obtained catalyst mud material with an extruder, placing on a stainless steel mesh plate, roll-coating, pleating, shearing, drying in air at 115 deg.C for 6min, and calcining in air at 780 deg.C for 5.5h to obtain 15% La 0.8 Sr 0.2 Co 0.57 Mo 0.43 O 3 /85％γ-Al 2 O 3 A flat catalyst with the components in percentage by mass;
the prepared flat-plate catalyst is prepared by mixing 10 percent by volume of CO and 2 percent by volume of SO 2 5% of O 2 And 83% of N 2 Treating the mixture in pre-sulfuration gas at 200 ℃ for 3.5 hours; then cutting off SO 2 Heating the gas to 350 ℃, and keeping the temperature for 3.5h; finally, the temperature is raised to 680 ℃, and SO is introduced 2 Keeping the gas for 3.5 hours to obtain the presulfurized flat catalyst.
The obtained catalyst component is La 15% by mass 0.8 Sr 0.2 Co 0.57 Mo 0.43 O 3 /85％γ-Al 2 O 3 。
The catalysts prepared in the previous examples 1 to 4 were subjected to CO and SO at 300 ℃ and 400 ℃ respectively 2 And NO x Synchronous removal test, the test working condition is: CO concentration 500mg/m 3 NO concentration 420mg/m 3 ，SO 2 The concentration is 450mg/m 3 ，O 2 Volume ratio of 5%, H 2 The volume ratio of O is 5 percent, and the space velocity is 4500h -1 . Removal testThe efficiency data obtained in the test are given in the following table:
TABLE 1.300 deg.C CO, SO 2 And NO x Synchronous stripping efficiency
Figure BDA0002534173990000091
TABLE 2 CO, SO at 450 deg.C 2 And NO x Synchronous stripping efficiency
Figure BDA0002534173990000092
Figure BDA0002534173990000101
As can be seen from the above tables 1 and 2, the catalyst provided by the embodiments of the present invention has good catalytic activity and anti-oxygen poisoning performance in the temperature range of 300-450 ℃, and can realize CO and SO 2 And NO x The high-efficiency synchronous removal is realized.
It should be understood that the above-mentioned embodiments are only for illustrating the technical concept and features of the present invention, and are not intended to be exhaustive or to limit the scope of the present invention, for providing those skilled in the art with understanding the present invention and implementing the same. Modifications and equivalents may be made thereto without departing from the spirit and scope of the invention, which is set forth in the claims.

Claims (6)

1. Flat plate type CO and SO 2 And NO x The preparation method of the synchronous removal catalyst is characterized by comprising the following steps:
step 1. Catalyst support preparation, comprising:
under the condition of stirring, adding AlCl 3 The solution is slowly dripped into NaOH solution to obtain transparent NaAlO 2 A solution; adding the hydrogen peroxide solution into a hexadecyl trimethyl ammonium bromide solution at the temperature of 45 ℃,after stirring evenly, naAlO is added 2 Slowly dripping the solution into hexadecyl trimethyl ammonium bromide solution, stirring uniformly, and then adding 30% of H 2 O 2 A solution; carrying out hydrothermal reaction on the obtained colloid at 40 ℃ for 12h, then carrying out reaction at 120 ℃ for 12h, washing the product with water, filtering, drying at 80-120 ℃ for 12-24h in the air, and then roasting at 500-550 ℃ for 4-24h in the air to obtain the gamma-Al-based composite material 2 O 3 A nanotube;
step 2, catalyst mud preparation, which comprises the following steps:
according to La 0.8 Sr 0.2 Co x Mo 1-x O 3 Sequentially adding lanthanum nitrate, strontium nitrate, cobalt nitrate and ammonium heptamolybdate into deionized water according to the proportion of the lanthanum, strontium, cobalt and molybdenum elements in the materials, adding citric acid after the lanthanum nitrate, strontium nitrate, cobalt nitrate and ammonium heptamolybdate are completely dissolved, and stirring for 1-2h at 40-60 ℃; adding the obtained solution into the gamma-Al prepared in the step 1 2 O 3 Uniformly stirring the nano tube, adding montmorillonite, glass fiber, polyethylene oxide and carboxymethyl cellulose, and aging for 24 to 48h under a closed condition to prepare a catalyst mud;
and 3, preparing a flat-plate catalyst, comprising the following steps:
and 31, forming the flat-plate catalyst, which comprises the following steps:
extruding the catalyst mud material prepared in the step 2 by an extruder, placing the extruded catalyst mud material on a stainless steel screen plate, rolling, coating, creasing and shearing, drying in the air at 105 to 120 ℃ for 5 to 10min, and roasting in the air at 750 to 800 ℃ for 4 to 8h to prepare a flat plate type catalyst;
step 32. Catalyst presulfiding, comprising:
the flat-plate catalyst prepared in the step 31 is prepared from CO and SO 2 、O 2 And N 2 Treating the pre-vulcanized gas at 200 ℃ for 1 to 4 hours; then cut off SO 2 Heating the gas to 300-400 ℃ and keeping the temperature for 1-4 h; finally heating to 600 to 700 ℃ and introducing SO 2 Keeping the gas for 2 to 6 hours to prepare the prevulcanized flat-plate La 0.8 Sr 0.2 Co x Mo 1-x O 3 /γ-Al 2 O 3 A catalyst,namely the flat plate type CO and SO 2 And NO x Synchronously removing the catalyst; the composition comprises 5 to 20 mass percent of La 0.8 Sr 0.2 Co x Mo 1-x O 3 And 80 to 95% of gamma-Al 2 O 3 A nanotube; the La 0.8 Sr 0.2 Co x Mo 1-x O 3 The structure is a perovskite structure, wherein the value of x is 0.5 to 0.7;
the gamma-Al 2 O 3 The length of the nano tube is 250 to 300nm, and the outer diameter of the nano tube is 18 to 20nm.
2. The method of claim 1, wherein the step 1 is performed using AlCl 3 The concentration of the solution is 0.5mol/L, the concentration of the NaOH solution is 4mol/L, and AlCl 3 And NaOH in a molar ratio of 1.
3. The method according to claim 1, wherein the concentration of the cetyltrimethylammonium bromide solution in the step 1 is 0.3mol/L.
4. The method according to claim 1, wherein the amount of the citric acid added to the deionized water in the step 2 is equal to the total amount of the metal ion species added.
5. The method according to claim 1, wherein the length of the glass fiber in the step 2 is 4 to 6mm.
6. The method of claim 1, wherein the pre-sulfiding gas in step 32 is CO, SO 2 、O 2 And N 2 The volume ratio of each component is respectively 10%, 2%, 5% and 83%.
CN202010527741.0A 2020-06-11 2020-06-11 Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof Active CN111744494B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010527741.0A CN111744494B (en) 2020-06-11 2020-06-11 Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010527741.0A CN111744494B (en) 2020-06-11 2020-06-11 Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111744494A CN111744494A (en) 2020-10-09
CN111744494B true CN111744494B (en) 2022-11-18

Family

ID=73451142

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010527741.0A Active CN111744494B (en) 2020-06-11 2020-06-11 Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111744494B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471589A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane
CN115518661B (en) * 2021-06-25 2023-12-05 中国石油化工股份有限公司 Sulfur-tolerant shift catalyst, preparation method and application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3342500A1 (en) * 1983-11-24 1985-06-13 Heinrich Dr.rer.nat. 8032 Gräfelfing Frühbuss METHOD FOR REMOVING SO (DOWN ARROW) X (DOWN ARROW) AND NO (DOWN ARROW) X (DOWN ARROW) FROM EXHAUST GAS
CN106268296B (en) * 2016-08-03 2019-06-14 中南大学 A kind of flue gas processing method of the lanthanum based perovskite type catalytic reduction of composite oxide simultaneous SO_2 and NO removal of doping
CN108355665A (en) * 2018-02-06 2018-08-03 北京石油化工学院 Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application
CN108722431B (en) * 2018-05-15 2021-06-18 昆明理工大学 A-site doped double perovskite catalyst and preparation method and application thereof

Also Published As

Publication number Publication date
CN111744494A (en) 2020-10-09

Similar Documents

Publication Publication Date Title
WO2015149499A1 (en) Low-temperature and highly efficient denitration catalyst and preparation method therefor
CN109731569B (en) Honeycomb type SCR denitration catalyst with three-dimensional multi-stage pore channel structure and preparation method thereof
CN102357364B (en) Preparation for the absorbent charcoal based catalyst of flue gas selective reduction desulfurization
CN107774270B (en) Preparation method of modified rare earth concentrate SCR denitration catalyst
CN108212169B (en) Preparation method of low-temperature denitration catalyst taking hydrotalcite as precursor
CN104014331B (en) The preparation method of the Mn-Ce-W composite oxides denitrating catalyst of mesoporous TiO 2 ball load
CN111744494B (en) Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof
CN110801848B (en) Flat plate type wide-temperature sulfur-resistant SCR denitration catalyst and preparation method thereof
CN112742413B (en) Low-temperature SCR denitration catalyst and preparation method and application thereof
CN113289609B (en) High-wear-resistance wide-temperature denitration catalyst and preparation method and application thereof
CN109225248A (en) Cellular low-temperature denitration catalyst and its preparation process
CN106466608B (en) Catalyst for catalytic reduction of nitrogen oxides by carbon monoxide and preparation method thereof
CN113996309B (en) Preparation method of high-strength SCR catalyst for CO-removal
CN109967069A (en) A kind of low-temperature SCR catalyst and preparation method thereof for cement kiln flue gas denitration
CN112973668A (en) High-strength honeycomb type low-temperature SCR denitration catalyst and preparation method thereof
CN109589967B (en) High-activity sulfur-resistant SCR denitration catalyst and preparation method thereof
CN112121872A (en) Forming process for low-temperature NOx rapid alternate adsorption-regeneration catalyst
CN108514881B (en) For NH3Catalytic oxidation Cu-Ce catalyst with nanorod-shaped structure, preparation method and application
CN103894184B (en) A kind of high-specific surface area vanadium zinc system's modification denitrating catalyst and preparation method
CN106423184A (en) Catalyst capable of removing N2O, NO and NO2 simultaneously and preparation method
CN112023908B (en) Nitrogen oxide removing catalyst and preparation method thereof
CN110694640B (en) Water-resistant sulfur-resistant denitration catalyst and preparation method thereof
CN111686745B (en) Honeycomb type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof
CN108816257B (en) Sulfur-resistant and water-resistant alkaline earth metal doped cerium phosphate-based catalyst and preparation method and application thereof
CN105664925A (en) Catalyst for low-temperature SCR denitration of cement kiln tail flue gas 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
GR01 Patent grant
GR01 Patent grant