CN109126815B - Low-temperature denitration catalyst and application - Google Patents

Low-temperature denitration catalyst and application Download PDF

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CN109126815B
CN109126815B CN201710497504.2A CN201710497504A CN109126815B CN 109126815 B CN109126815 B CN 109126815B CN 201710497504 A CN201710497504 A CN 201710497504A CN 109126815 B CN109126815 B CN 109126815B
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catalyst
low
flue gas
temperature
denitration
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CN109126815A (en
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王昊辰
李欣
姜阳
王宽岭
王明星
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • B01D53/8637—Simultaneously removing sulfur oxides 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
    • B01D53/90—Injecting reactants
    • 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
    • B01J35/615—
    • B01J35/635—
    • B01J35/638—
    • B01J35/69—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • 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

Abstract

The invention discloses a low-temperature denitration catalyst and application thereof, wherein the low-temperature denitration catalyst comprises the following components in parts by weight: 75% -94% of alumina carrier and 3% -20% of Fe2O3And 3% -20% MnO2(ii) a The catalyst is microspherical, the diameter of the catalyst is 2-6 mm, the total porosity is 60% -85%, in all pores, the proportion of 5-20 nm mesopores to the total porosity is 15% -55%, and the proportion of 100-1000 nm macropores to the total porosity is 40% -75%; the macropores are uniformly distributed and are communicated in a three-dimensional way; the side pressure crushing strength is 5-20N/mm. The catalyst provided by the invention is applied to low-temperature denitration reaction, can effectively remove nitrogen oxides and sulfur oxides in flue gas, does not cause the problem that ammonium bisulfate blocks a bed layer, and prolongs the operation period of a device.

Description

Low-temperature denitration catalyst and application
Technical Field
The invention belongs to the technical field of flue gas denitration, and particularly relates to a low-temperature denitration catalyst and application thereof.
Background
Nitrogen oxides, collectively referred to as NOx, are one of the main sources of atmospheric pollution. The most harmful are: NO, NO2. The major hazards of NOx are as follows: (1) has toxic effect on human body; (2) has toxic action on plants; (3) acid rain and acid mist can be formed; (4) forming photochemical smog with hydrocarbon; (5) and destroying the ozone layer.
The flue gas denitration refers to removing NOx in flue gas, and can be divided into wet denitration and dry denitration according to treatment processes. The method mainly comprises the following steps: acid absorption, alkali absorption, selective catalytic reduction, non-selective catalytic reduction, adsorption, plasma activation, and the like. Some researchers at home and abroad have also developed a method for treating NOx waste gas by using microorganisms. But is of industrial value and the most widely used is the Selective Catalytic Reduction (SCR) process.
At present, the denitration treatment of flue gas of a coal-fired power plant and FCC regenerated flue gas of an oil refinery mainly adopts an SCR method and is matched with wet washing, desulfurization and dust removal. Taking FCC flue gas as an example, the main flow is as follows: the method comprises the steps that FCC regenerated flue gas at 500-600 ℃ is subjected to heat recovery through a waste heat boiler, the temperature of the flue gas is reduced to 320-400 ℃, the flue gas enters an SCR fixed bed reactor for denitration reaction, NOx in the flue gas is removed, then the flue gas returns to the waste heat boiler to recover heat, the temperature of the flue gas is reduced to 150-200 ℃, then the flue gas enters a desulfurization and dedusting washing tower, SOx and dust in the flue gas are washed down by adopting alkaline absorption liquid, and the temperature of the flue gas is reduced to 55-60 ℃ and is discharged. And (3) carrying out liquid-solid separation on the desulfurization waste absorption liquid by the steps of settling, filtering, concentrating and the like, wherein the liquid after the liquid-solid separation is oxidized by adopting air aeration, COD (chemical oxygen demand) reaches the standard and is discharged, and the solid is buried.
The existing SCR denitration process adopts a fixed bed denitration reactor, a catalyst adopts a honeycomb type, a plate type or a corrugated type, and the catalyst is placed in the reactor in a module form. Firstly injecting reducing agent NH in front of the reaction bed layer3Let NH3Fully mixed with NOx in the flue gas, and the NOx is catalytically reduced into N through a denitration catalyst bed layer2。
The prior art has the following problems:
1. because the flue gas generally contains SO2、SO3，O2With water vapor, SO when the reaction zone has excess ammonia (ammonia slip)3Reacting to form ammonium salt, and forming ammonium salt (NH)4HSO4) The liquid-state heat exchange tube is liquid at the temperature of 180-240 ℃, has viscosity, is easy to attach to a heat exchange tube of a coal economizer of a downstream device of the SCR denitration reactor, bonds dust in flue gas, causes scaling blockage and corrosion of the heat exchange tube layer, and affects the operation period of the device. In order to avoid ammonia escape, the uniformity of ammonia injection at the inlet of the SCR fixed bed reactor generally requires that the plus-minus deviation is less than 5%.
2. The content of NOx in the flue gas is related to the process conditions of a main device, the variation fluctuation range is large, the amount of the catalyst of the SCR fixed bed reactor is fixed, and once the concentration range of the NOx exceeds the designed value, the NOx in the purified flue gas cannot reach the standard and is discharged. The fixed bed is therefore less flexible to operate.
3. During the operation of the fixed bed reactor, the activity of the catalyst is gradually reduced, and when NOx at the outlet of the reactor cannot reach the standard and is discharged, the catalyst needs to be replaced. Typically, the operating cycle of an SCR device requires at least 3-4 years, otherwise the operation of the main device may be affected. The denitration rate of a common SCR device is required to be at least more than 60-90%, and when the catalyst is replaced, the activity of the catalyst is at least about 60%. It follows that the utilization of the catalyst is too low with a fixed bed SCR reactor.
4. After the denitration of the general flue gas, wet washing and dust removal are adopted and are carried out together with desulfurization, and the desulfurization waste liquid generated in the desulfurization and dust removal process is subjected to liquid-solid separation, so that the process is complicated, the operation is complex, and the investment and the operation cost are high.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a low-temperature denitration catalyst and application thereof. The microspherical low-temperature denitration catalyst with abundant macropores can effectively improve the reaction space of the catalyst and the capability of resisting fly ash and salt poisoning.
The low-temperature denitration catalyst comprises the following components in percentage by weight: 75% -94% of alumina carrier and 3% -20% of Fe2O3And 3% -20% MnO2(ii) a The catalyst is microspherical, the diameter of the catalyst is 2-6 mm, the preferable diameter is 3-5 mm, the total porosity is 60% -85%, in all pores, the proportion of 5-20 nm mesopores to the total porosity is 15% -55%, and the proportion of 100-1000 nm macropores to the total porosity is 40% -75%; the macropores are uniformly distributed and are communicated in a three-dimensional way; the side pressure crushing strength is 5 to 20N/mm, preferably 8 to 18N/mm.
The BET specific surface area of the denitration catalyst is 120-400 m2Per g, pore volume of 0.45-1.50 cm3/g。
The catalyst can also contain one or more of auxiliary agents such as Zr, Ce or Cu, preferably Zr, wherein the auxiliary agent accounts for 1-10% of oxide by taking the total weight of the catalyst as a reference, and the sum of the contents of all components in the catalyst is 100%.
The preparation method of the low-temperature denitration catalyst comprises the following steps:
(1) dissolving an aluminum source, polyethylene glycol and an organic compound containing an amide group in a low-carbon alcohol aqueous solution, and uniformly mixing to obtain a clear solution; adding pyridine into the mixture obtained in the step (1), and uniformly mixing; wherein the viscosity-average molecular weight of the polyethylene glycol is 10000-3000000, preferably 100000-2000000;
(2) dripping the obtained mixture into an oil column at the temperature of 20-50 ℃ to form a microspherical alumina carrier, aging at the temperature of 40-80 ℃ for 12-60 hours, soaking an aged product by using low carbon alcohol or low carbon alcohol aqueous solution, then carrying out solid-liquid separation, drying and roasting a solid phase to obtain the microspherical alumina carrier;
(3) and (3) impregnating the alumina carrier with soluble salt containing Mn and Fe, and then drying and roasting to obtain the microspherical denitration catalyst.
The weight of the mixture obtained in the step (1) is taken as a reference, the adding amount of the low-carbon alcohol aqueous solution is 10-80%, the adding amount of the aluminum source is 10-20%, and the adding amount of the polyethylene glycol is 0.1-3.0%, preferably 0.2-2.0%; wherein the mass ratio of water to the low-carbon alcohol in the low-carbon alcohol aqueous solution is 1.0-1.3; the molar ratio of the polyethylene glycol to the amide group-containing organic compound is 0.05 to 1.0, preferably 0.1 to 0.8; pyridine and Al3+The molar ratio of (A) to (B) is 3.0 to 9.0, preferably 3.5 to 7.0.
The aluminum source in the step (1) is one or more of aluminum nitrate, aluminum chloride and aluminum sulfate.
The lower alcohol in the steps (1) and (2) is generally C5The alcohol is preferably one or more of methanol, ethanol, n-propanol and isopropanol, and most preferably ethanol and/or propanol.
The organic compound containing amide groups in the step (1) is selected from one or more of formamide and N, N-dimethylformamide.
The soaking conditions in the step (2) are as follows: the soaking temperature is 10-80 ℃, and the soaking time is 24-48 hours.
The drying in the step (2) is ordinary normal pressure drying, the drying temperature is not more than 60 ℃, preferably 20-40 ℃, and the drying is carried out until no obvious liquid exists. The roasting is carried out at 400-950 ℃ for 1-24 hours, preferably at 550-850 ℃ for 5-10 hours.
And (3) the soluble salt of Mn is manganese nitrate, and the soluble salt of Fe is ferric nitrate. When the promoter is present in the catalyst, it may be introduced during step (3). And (4) the soluble salt solution of Mn and Fe in the step (3) is prepared according to the composition calculation of the target catalyst. The method can adopt modes of over-volume impregnation, equal-volume impregnation or spray impregnation and the like, and the impregnation time is 1-5 hours. The drying conditions in the step (3): the drying temperature is 100-130 ℃, and the drying time is 1-10 hours; the roasting conditions are as follows: the roasting temperature is 450-600 ℃, and the roasting time is 2-6 hours.
In the preparation process of the catalyst, the polyethylene glycol and the amide group-containing organic compound are introduced in a specific ratio to meet the characteristic of forming the macropores. The concentrated mesopores of the invention are derived from a sol-gel network, and the abundant and through macropores are derived from solid-liquid two-phase separation caused by polyethylene glycol. By adding the amide substance and adjusting the sol-gel process of the system, a more uniform sol-gel system can be generated, so that a more uniform, i.e. more concentrated mesoporous distribution gel material can be obtained after roasting.
On the basis of the formation of the mesoporous gel, the polyethylene glycol is distributed in the mesoporous gel more uniformly and finely. The method comprises the following steps of adding pyridine, increasing the pH value in a reaction system, releasing a certain amount of ammonia from an organic compound containing an amide group, enabling the alkaline effect of a liquid phase of the system to be more obvious, changing polyethylene glycol in the liquid phase from a relatively stretched state to a relatively contracted state under an alkaline environment, reducing the pore-forming range of a space of the liquid phase, generating macropores with relatively small pore diameters and more numbers, enabling the macropores with relatively small sizes to be mutually communicated, soaking the liquid phase by using low-carbon alcohol or low-carbon alcohol aqueous solution after aging to remove liquid phases such as polyethylene glycol and the like, enabling the space occupied by the original liquid phase to be a pore channel with mutually communicated macroporous alumina, enabling the original solid phase part to form the pore wall of the macropore, improving the porosity of the alumina, and enabling the pore structure of the alumina to be.
The invention can adjust the sol-gel process of the system by introducing the amide group, generate more uniform sol-gel system, and reduce the solid-liquid phase separation degree, thereby correspondingly reducing the aperture of the macropore. The effect can be uniform in stress distribution during drying and roasting at normal pressure, the integrity of the macropores is kept, the material is prevented from being broken, and the integral mechanical strength of the material is improved. The invention adopts higher alcohol-water mixture and higher aging temperature in the aging stage, can cause the gel particles to generate hydration reaction, enhances the bonding strength among the particles, greatly shrinks the system when being dried and roasted under normal pressure, and relatively improves the compactness, thereby further improving the mechanical strength.
The low-temperature denitration catalyst can be applied to a flue gas denitration reaction process. The following application procedure is preferably employed: low-temperature flue gas enters from the top of the denitration reactor, mixed gas containing ammonia gas is injected into the flue gas through an ammonia injection grid, the air flow passes through a plurality of layers of horizontally staggered catalyst bed layers from top to bottom to carry out denitration and desulfurization reactions to remove NOx and SOx, and ammonium salt (NH) generated by desulfurization4HSO4) The dust in the flue gas is filtered and adhered by the catalyst bed layer at the same time, and the purified flue gas is discharged from the bottom of the reactor; the catalyst bed layer comprises a reticular conveyor belt and low-temperature denitration catalysts stacked on the conveyor belt, the running directions of the adjacent upper and lower layers of conveyor belts are opposite, the upper-layer low-temperature denitration catalysts move to the tail end of the conveyor belt along with the conveyor belt and freely fall to the starting end of the running direction of the lower-layer conveyor belt by means of gravity, the low-temperature denitration catalysts fall into a catalyst hopper at the tail end of the last layer of conveyor belt, and ammonium salts are removed through stripping and are recycled.
The flue gas mainly comprises flue gas of a coal-fired power plant, FCC regenerated flue gas, flue gas of an oil refinery process furnace or flue gas of a chemical industry furnace (such as flue gas of an ethylene cracking furnace) and the like. The flue gas mainly contains NOx, SOx and impurities, wherein the impurities are dust, water and CO2And O2Etc., wherein the concentration of NOx is generally 700 to 4500mg/Nm3The concentration of SOx is generally 700-4500 mg/Nm3(ii) a The temperature of the low-temperature flue gas entering the denitration reactor is 150-260 ℃, and preferably 180-240 ℃.
The flow velocity of the flue gas is 2-15 m/s, and preferably 4-10 m/s; the residence time of the denitration reaction is 0.5-20 s.
In the mixed gas containing ammonia gas filled by the ammonia injection grid, the total molar ratio of the ammonia gas to NOx and SOx in the flue gas is 0.9: 1-1.15: 1.
the mixed gas containing ammonia gas is a mixture of ammonia gas and air, wherein the volume concentration of the ammonia gas in the mixed gas is 0.5% -10%. In the method, the conveyor belt is a conventional metal mesh conveyor belt, preferably a stainless steel mesh conveyor belt, the mesh size of the conveyor belt is ensured to be smaller than the size of catalyst particles so as to ensure that the catalyst particles do not fall off the meshes, and the mesh size is generally 0.1-3 mm, preferably 1.5-2.5 mm; the conveyer belt adopts external motor drive, is driven the conveyer belt rotation by the conveyer belt drive wheel.
The stacking height of the low-temperature denitration catalyst on the conveyor belt is 50-500 mm, and preferably 200-300 mm.
The conveying speed of the conveying belt is 0.1-10 mm/s, preferably 0.5-2 mm/s.
The number of layers and the width of the conveying belt can be selected according to actual needs and the size of the reactor, the number of layers of the conveying belt is preferably 3-10 layers, more preferably 3-8 layers, the width of the conveying belt is limited by not touching the wall of the reactor, and the gap between the width direction of the conveying belt and the wall of the reactor is 2-50 mm, preferably 2-5 mm.
The vertical distance between two adjacent layers of conveyor belts is 1200-2000 mm, preferably 1400-1600 mm.
The catalyst dropped into the catalyst hopper is stripped and then returns to the top to be filled into the first layer of the conveyor belt to complete the circulation of the catalyst.
The stripping is carried out in a stripper, and the stripping process comprises the following steps: introducing medium and low pressure steam from the bottom, introducing catalyst adhered with ammonium salt from the top, gasifying and taking out ammonium salt in the catalyst by using the medium and low pressure steam, gasifying and decomposing the ammonium salt to obtain SO2、NH3、H2O and the likeAnd the mixed gas enters a condenser to react to an ammonium salt solution.
Compared with the prior art, the invention has the following advantages:
(1) in the invention, NOx and SOx in the flue gas directly react with the mixed gas containing ammonia gas, and the NOx is reduced into N2SOx directly generates ammonium salt, the ammonium salt is a sticky liquid substance at the temperature and is adhered to the catalyst, dust in the flue gas is adhered to catalyst particles along with the ammonium salt and leaves the reaction system together with the catalyst particles, so that the effect of dust removal is achieved, denitration, desulfurization and dust removal can be completed in one reactor, subsequent processes are reduced, investment and operating cost are reduced, and meanwhile, low-temperature reaction is adopted, so that energy consumption and requirements on equipment are reduced. The invention adopts the microspherical catalyst bed layer to filter dust in the flue gas, and the catalyst has double-hole distribution, so that the dust smaller than 1 micron can be better captured, and the blockage is not easy to occur.
(2) According to the invention, the conveyor belt is adopted to form a moving catalyst bed layer, the generated ammonium salt is adhered to catalyst particles and leaves a reaction system together with the catalyst particles, so that the problem that the bed layer is blocked by ammonium bisulfate due to ammonia escape is avoided, and the operation period of the device is prolonged;
(3) the invention can adjust the residence time of the catalyst in the reactor by adjusting the movement speed of the conveyor belt, and adjust the reaction time of the flue gas passing through the catalyst bed by adjusting the height of the catalyst bed on the conveyor belt, so that the invention can treat the flue gas with different NOx and SOx concentrations and is more suitable for FCC regenerated flue gas with high NOx concentration;
(4) the catalyst is recycled, the reacted catalyst is stripped to remove ammonium salt and then is fed back to the first layer of the conveyor belt for continuous reaction, so that the using amount of the catalyst can be greatly reduced, and the ammonium salt obtained by stripping can be used as a byproduct of a denitration reaction.
Drawings
FIG. 1 is a schematic view of a denitration catalyst application process of the present invention.
1. Flue gas, 2, mixed gas containing ammonia gas, 3, catalyst particles, 4, purified gas, 5, stripping gas, 6, ammonium salt steam, 7, ammonium salt solution, 8, an ammonia spraying grid, 9, a catalyst adding pipe, 10, a conveyor belt, 11, a conveyor belt driving wheel, 12, a catalyst discharging pipe, 13, a catalyst hopper, 14, a reactor inner cylinder, 15, a reactor shell, 16, a stripper, 17 and a condenser.
FIG. 2 scanning electron micrograph of inventive example 1 catalyst.
Detailed Description
The process of the present invention is illustrated in detail below by means of specific examples, without thereby restricting the invention. The pore distribution and porosity are characterized by mercury intrusion method, the mechanical strength is characterized by side pressure crushing strength, and the strength is measured by ZQJ-II intelligent particle strength tester produced by large-scale equipment diagnotor factory.
The invention also provides a denitration reactor, which comprises a condenser 17, a stripper 16, a reactor shell 15, a reactor inner cylinder 14, an ammonia spraying grid 8, a catalyst adding pipe 9, a conveyor belt 10, a conveyor belt driving wheel 11, a catalyst discharging pipe 12 and a catalyst hopper 13; the reactor outer sealing cavity is arranged between the reactor outer shell 15 and the reactor inner cylinder 14, the conveyor belt driving wheel 11 is arranged in the reactor outer sealing cavity, the conveyor belt 10 is attached to the conveyor belt driving wheel 11 and traverses the reactor inner cylinder 14, the catalyst adding pipe 9 is arranged at the top of the reactor outer sealing cavity, the outlet at the bottom of the catalyst adding pipe 9 is opposite to one end of the conveyor belt, the catalyst hopper 13 is arranged at the bottom of the reactor outer sealing cavity, the catalyst discharging pipe 12 is connected to the bottom of the catalyst hopper 13, the outlet at the bottom of the catalyst discharging pipe 12 is opposite to the stripper 16, the solid outlet of the stripper 16 is connected with the catalyst adding pipe 9, and the gas outlet of the.
The operation process of the denitration reactor is as follows: the microspherical denitration catalyst 3 is injected onto a first layer of conveyor belt 10 through a catalyst adding pipe 9 and is accumulated to form a bed layer, a conveyor belt driving wheel 11 drives the bed layer on the conveyor belt 10 to move, the bed layer penetrates through an inner cylinder 14 of the reactor and enters an outer sealing cavity of the reactor, and falls onto the next conveyor belt under the action of gravity to form a bed layer, and the bed layer moves in the opposite direction under the driving of the conveyor belt driving wheel 11 to form a continuous running conveyor belt bed layer according to the running mode; flue gas 1 enters from the bottom of a reactor, mixed gas 2 containing ammonia is injected into the flue gas 1 through an ammonia injection grid 8, airflow passes through a plurality of layers of horizontally staggered catalyst bed layers from top to bottom to perform denitration and desulfurization reactions, NOx and SOx are removed, dust adheres to catalyst particles along with ammonium salt, the obtained purified gas 4 is discharged from the bottom of the reactor, the catalyst falls into a catalyst hopper 13 at the tail end of the last layer of conveyor belt 10 and enters a stripper 16 through a catalyst discharge pipe 12, stripped ammonium salt steam 6 is condensed through a condenser 17 to obtain an ammonium salt solution 7, and the stripped catalyst particles return to a catalyst adding pipe 9 and are injected onto the first layer of conveyor belt 10 to complete circulation.
Example 1
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol and formamide at room temperature (20 ℃), and then adding pyridine, wherein the mixture comprises the following components in parts by weight: 23% of water, 22% of ethanol, 20% of aluminum chloride, 0.3% of polyethylene glycol (viscosity-average molecular weight is 100 ten thousand), 1% of formamide and 33.7% of pyridine. And after uniform mixing, dropwise adding the obtained mixture into an oil column at 20-50 ℃ to form microspheres, aging at 45 ℃ for 48 hours, soaking the aged mixture for 48 hours by using a mixed solution of ethanol and water, removing a liquid phase after soaking, and drying at 40 ℃ until the product is not obviously reduced. Then roasting for 6 hours at 600 ℃ to obtain a microsphere alumina carrier; and (2) impregnating the alumina carrier with an impregnating solution containing ferric nitrate and manganese nitrate in equal volume, drying at 80 ℃ for 8 hours, roasting at 550 ℃ for 6 hours, and cooling to room temperature to obtain the microspherical denitration catalyst A.
MnO210wt% of Fe2O3The content is 5wt%, the total porosity is 80%, the pores have double pore distribution, wherein the macropores are uniformly distributed, the average pore diameter of the macropores is 360nm, and the macropore porosity accounts for 55%; the mesoporous aperture is 4-6 nm, and the mesoporous porosity accounts for 24%. The lateral pressure strength is 7.1N/mm, the BET specific surface area is 160m2Per g, pore volume of 0.51cm3(ii) in terms of/g. The observation of a scanning electron microscope shows that the macropore has three-dimensional connectivity.
Example 2
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol and formamide at room temperature (20 ℃), and then adding pyridine, wherein the mixture comprises the following components in parts by weight: 31% of water, 29% of ethanol, 16% of aluminum chloride, 0.5% of polyethylene glycol (viscosity-average molecular weight is 200 ten thousand), 3.5% of formamide and 20% of pyridine. And after uniform mixing, dropwise adding the obtained mixture into an oil column at 20-50 ℃ to form microspheres, aging at 60 ℃ for 24 hours, soaking the aged mixture in ethanol for 48 hours, removing a liquid phase after soaking, and drying at 50 ℃ until the product is not obviously reduced in weight any more. Then roasting for 5 hours at 750 ℃ to obtain a microspherical alumina carrier; and (2) impregnating the alumina carrier with an impregnating solution containing ferric nitrate and manganese nitrate in equal volume, drying at 100 ℃ for 5 hours, roasting at 550 ℃ for 5 hours, and cooling to room temperature to obtain the microspherical denitration catalyst B.
MnO28wt% of Fe2O3The content is 12wt%, the total porosity is 73%, the pores have double pore distribution, the macropores are uniformly distributed, the average pore diameter of the macropores is 180nm, and the macropore porosity accounts for 47%; the mesoporous aperture is 7-11 nm, and the mesoporous porosity accounts for 31%. Lateral pressure strength 8.9N/mm. BET specific surface area of 155 m2Per g, pore volume of 0.61cm3(ii) in terms of/g. The observation of a scanning electron microscope shows that the macropore has three-dimensional connectivity.
Comparative example 1
This example is compared with example 1. Except that formamide was not added. The average macropore diameter is 4.6 μm, the porosity is 45%, and the macropore porosity accounts for 13%. Pore size distribution: the mesopores are 4-20nm, and the macropores are 3.1-7.9 μm. Lateral pressure strength 1.3N/mm. The BET specific surface area of the obtained material was 115 m2Per g, pore volume of 0.4 cm3(ii) in terms of/g. The observation of a scanning electron microscope shows that the macropores are basically isolated, and the distribution of the macropores is not uniform.
Example 3
The flow rate of FCC regeneration flue gas is 15 ten thousand Nm3At 650 ℃ and a pressure of 10kPa, and a NOx concentration of 600mg/Nm3，SO2The concentration is 1000mg/Nm3，SO3The concentration is 20mg/Nm3Dust content of 200mg/Nm3. NOx emission standard is 200mg/Nm3。
The catalyst adopts a microspherical denitration catalyst A.
Firstly, FCC regeneration flue gas is heated by a boiler, the temperature is reduced from 650 ℃ to 200 ℃ and the flow rate of the mixture containing ammonia gas is 1800Nm3The volume fraction of ammonia gas is 4%, the stripping gas is 0.8MPa and superheated steam at 420 ℃, and the flow rate is 15Nm3The embodiment adopts a movable reactor, the size of an inner sealed cavity of the reactor is 8m in length, × in width, 6m in width, × in height and 8m in height, the reaction time is 0.5s, 3 layers of conveyor belts are arranged, the height of a catalyst bed on each conveyor belt is 300mm, the size of each conveyor belt is 9m, × in length and 5.8m in width, a stainless steel mesh conveyor belt is selected, the diameter of a gap is 3mm, the diameter of a driving wheel is 300mm, the space between the upper layer of conveyor belt and the lower layer of conveyor belt is 1300mm in height, and enough maintenance space is reserved3，SO2The content is 25mg/Nm3Dust content of less than 10mg/Nm3Meets the environmental protection requirement of key control areas, and the smoke can be discharged through a chimney.
Example 4
The FCC regeneration flue gas flow, temperature and pressure were the same as in example 3, and the NOx concentration was 2000mg/Nm3，SO2The concentration is 2000mg/Nm3，SO3The concentration is 200mg/Nm3Dust content of 400mg/Nm3. NOx emission standard is 100mg/Nm3。
The catalyst adopts a microspherical denitration catalyst B.
Firstly, heating FCC (fluid catalytic cracking) regenerated flue gas by a boiler, and reducing the temperature from 650 ℃ to 200 ℃ of SCR denitration reaction; the flow rate of the ammonia-containing mixture is 1600Nm3The volume fraction of ammonia gas is 3%, the stripping gas is 0.8MPa and superheated steam at 420 ℃, and the flow rate is 15Nm3H, the size of an inner sealing cavity of the reactor is 8m in length, × in width, 6m in width, × in height and 15m in height, the reaction time is 2s, 10 layers of conveyor belts are arranged, the height of a catalyst bed on each conveyor belt is 500mm, the size of each conveyor belt is 9m, × in length, 5.8m in width, a stainless steel mesh conveyor belt is selected, the diameter of a gap is 3mm, the diameter of a driving wheel is 300mm, the space between the upper layer of conveyor belt and the lower layer of conveyor belt is 1500mm, and enough maintenance space is leftThe amount is 100mg/Nm3，SO2The content is 30mg/Nm3Dust content of less than 10mg/Nm3Meets the environmental protection requirement of key control areas, and the smoke can be discharged through a chimney.
Comparative example 2
The same as example 3, except that the reactor was replaced by a conventional fixed bed reactor, the catalyst was a commercially available vanadium tungsten titanium honeycomb catalyst, the components of which are well known in the art, the catalyst was packed in a modular manner, the height of a single catalyst module was 1m, the size of the reactor was 4.4m × 4.6.6 m, the catalyst was packed in three layers, the FCC regeneration flue gas was first heated by a boiler, the temperature was reduced from 650 ℃ to 200 ℃ for SCR denitration reaction, and the flow rate of the ammonia-containing mixture supplied from the raw material supply zone was 1600Nm3H, ammonia concentration 3 v%. The mixed gas containing ammonia gas is added into an upstream flue at a certain distance from the inlet of the reactor, the ammonia gas concentration deviation in the flue gas at the inlet of the reactor is ensured to be less than 5 percent after the mixed diffusion of an ammonia spraying grid, the mixed gas enters the SCR reactor for reaction, and the NOx content of the purified flue gas can be ensured to be 100mg/Nm after the denitration reaction3And the denitrated flue gas continuously enters a downstream device for heat exchange, desulfurization and dust removal, so that the environmental protection requirement of key control areas is met.
Comparative example 3
The reactor in comparative example 2 was still used, the flue gas composition was the same as in example 4, and the concentration of NOx in the flue gas was too high, so that the ammonia escape was ensured to be less than 3mgNm3And the concentration of NOx after denitration is 1000-1300 mg/Nm3And the dust can not be discharged up to the standard, and the dust still needs to enter a desulfurization and dust removal system for treatment.
Comparative example 4
The same as example 3, except that the reactor is replaced by a traditional fixed bed reactor, the NOx content of the purified flue gas is ensured to reach the standard.
Comparative example 5
The same as example 4 except that the reactor was replaced with a moving bed reactor in CN 102008893A. Selecting a catalyst with the particle size of 2.5-7.5 mm, wherein the catalyst is in the shape of particles, short columns or honeycombs and the like, the components are well known in the art, and the total circulation amount is 40m3The reactor size was 4.4m × 46m, NH added3The mol ratio of the catalyst to NOx in the flue gas is 1:1, the catalyst layer is uniformly mixed and enters the catalyst layer, and the flue gas from which NOx is removed is discharged from the upper part. After the denitration reaction, the NOx content of the purified flue gas can be ensured to be 100mg/Nm3And the denitrated flue gas continuously enters a downstream device for heat exchange, desulfurization and dust removal, so that the environmental protection requirement of key control areas is met. The operation period, the amount of the catalyst used and the purification effect of the examples and comparative examples are shown in Table 1.
Table 1 the examples are compared with comparative examples for run length, catalyst amount and purification effect.
Figure 180599DEST_PATH_IMAGE001

Claims (22)

1. A low-temperature denitration catalyst is characterized in that: based on the weight of the catalyst, the catalyst comprises the following components: 75% -94% of alumina carrier and 3% -20% of Fe2O3And 3% -20% MnO2(ii) a The catalyst is microspherical, the diameter of the catalyst is 2-6 mm, the total porosity is 60% -85%, in all pores, the proportion of 5-20 nm mesopores to the total porosity is 15% -55%, and the proportion of 100-1000 nm macropores to the total porosity is 40% -75%; the macropores are uniformly distributed and are three-dimensionally communicated.
2. The low-temperature denitration catalyst according to claim 1, characterized in that: the side pressure crushing strength is 5-20N/mm.
3. The low-temperature denitration catalyst according to claim 1, characterized in that: the BET specific surface area of the low-temperature denitration catalyst is 120-400 m2Per g, pore volume of 0.45-1.50 cm3/g。
4. The low-temperature denitration catalyst according to claim 1, characterized in that: the catalyst contains one or more of Zr, Ce or Cu auxiliaries, wherein the auxiliaries are 1-10% by weight of oxides based on the total weight of the catalyst, and the sum of the contents of all components in the catalyst is 100%.
5. A preparation method of a low-temperature denitration catalyst comprises the following steps: (1) dissolving an aluminum source, polyethylene glycol and an organic compound containing an amide group in a low-carbon alcohol aqueous solution, and uniformly mixing to obtain a clear solution; adding pyridine into the clarified solution, and uniformly mixing to obtain a mixture; wherein the viscosity average molecular weight of the polyethylene glycol is 10000-3000000; (2) dripping the obtained mixture into an oil column at the temperature of 20-50 ℃ to form a microspherical alumina carrier, aging at the temperature of 40-80 ℃ for 12-60 hours, soaking an aged product by using low carbon alcohol or low carbon alcohol aqueous solution, then carrying out solid-liquid separation, drying and roasting a solid phase to obtain the microspherical alumina carrier; (3) impregnating an alumina carrier with soluble salt containing Mn and Fe, and then drying and roasting to obtain a microspherical denitration catalyst; the organic compound containing amide groups is one or more of formamide and N, N-dimethylformamide; the molar ratio of the polyethylene glycol to the amide group-containing organic compound is 0.05-1.0; the aluminum source is one or more of aluminum nitrate, aluminum chloride and aluminum sulfate.
6. The method of claim 5, wherein: the weight of the mixture obtained in the step (1) is taken as a reference, the adding amount of the low-carbon alcohol aqueous solution is 10-80%, the adding amount of the aluminum source is 10-20%, and the adding amount of the polyethylene glycol is 0.1-3.0%; wherein the mass ratio of water to the low-carbon alcohol in the low-carbon alcohol aqueous solution is 1.0-1.3; the molar ratio of the pyridine to the aluminum source is 3.0-9.0, and the aluminum source is Al3+And (6) counting.
7. The method of claim 5, wherein: the lower alcohol in the steps (1) and (2) is C5 or less.
8. The method of claim 5, wherein: the soaking conditions in the step (2) are as follows: the soaking temperature is 10-80 ℃, and the soaking time is 24-48 hours.
9. The application of the low-temperature denitration catalyst of any one of claims 1 to 4 in flue gas denitration reaction.
10. Use according to claim 9, characterized in that: low-temperature flue gas enters from the top of a denitration reactor, mixed gas containing ammonia gas is injected into the flue gas through an ammonia injection grid, the air flow passes through a plurality of layers of horizontally staggered catalyst bed layers from top to bottom to carry out denitration and desulfurization reactions to remove NOx and SOx, ammonium salt generated by desulfurization is adhered to low-temperature denitration catalyst particles, dust in the flue gas is filtered by the catalyst bed layers to be adhered and dedusted, and purified flue gas is discharged from the bottom of the reactor; the catalyst bed layer comprises a reticular conveyor belt and low-temperature denitration catalysts stacked on the conveyor belt, the running directions of the adjacent upper and lower layers of conveyor belts are opposite, the upper-layer low-temperature denitration catalysts move to the tail end of the conveyor belt along with the conveyor belt and freely fall to the starting end of the running direction of the lower-layer conveyor belt by means of gravity, the low-temperature denitration catalysts fall into a catalyst hopper at the tail end of the last layer of conveyor belt, and ammonium salts are removed through stripping and are recycled.
11. Use according to claim 10, characterized in that: the concentration of NOx in the flue gas is 700-4500 mg/Nm3The concentration of SOx is 700-4500 mg/Nm3。
12. Use according to claim 10, characterized in that: the temperature of the low-temperature flue gas entering the denitration reactor is 150-260 ℃.
13. Use according to claim 10, characterized in that: the flow velocity of the flue gas is 2-15 m/s; the residence time of the denitration reaction is 0.5-20 s.
14. Use according to claim 10, characterized in that: in the mixed gas containing ammonia gas filled by the ammonia injection grid, the total molar ratio of the ammonia gas to NOx and SOx in the flue gas is 0.9: 1-1.15: 1.
15. use according to claim 10, characterized in that: the mixed gas containing ammonia gas is a mixture of ammonia gas and air, wherein the volume concentration of the ammonia gas in the mixed gas is 0.5% -10%.
16. Use according to claim 10, characterized in that: the conveyer belt adopt the netted conveyer belt of metal, conveyer belt mesh size guarantees to be less than catalyst particle size to guarantee that catalyst particle does not drop from the mesh, the conveyer belt adopts external motor drive, drives the conveyer belt rotation by the conveyer belt drive wheel.
17. Use according to claim 10, characterized in that: the stacking height of the low-temperature denitration catalyst on the conveying belt is 50-500 mm.
18. Use according to claim 10, characterized in that: the conveying speed of the conveying belt is 0.1 mm/s-10 mm/s.
19. Use according to claim 10, characterized in that: the number of the conveying belt layers is 3-10.
20. Use according to claim 10, characterized in that: the vertical distance between two adjacent layers of conveyor belts is 1200-2000 mm.
21. Use according to claim 10, characterized in that: the catalyst dropped into the catalyst hopper is stripped and then returns to the top to be filled into the first layer of the conveyor belt to complete the circulation of the catalyst.
22. Use according to claim 10, characterized in that: the stripping is carried out in a stripper, and the stripping process comprises the following steps: introducing medium and low pressure steam from the bottom, introducing catalyst adhered with ammonium salt from the top, gasifying and taking out ammonium salt in the catalyst by using the medium and low pressure steam, gasifying and decomposing the ammonium salt to obtain SO2、NH3、H2And O, introducing the mixed gas into a condenser to react to obtain an ammonium salt solution.
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