CN111167452B - Manufacturing method of catalyst carrier for marine diesel engine tail gas - Google Patents
Manufacturing method of catalyst carrier for marine diesel engine tail gas Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 22
- 239000004964 aerogel Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000499 gel Substances 0.000 claims description 13
- 230000006698 induction Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 150000002924 oxiranes Chemical class 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011240 wet gel Substances 0.000 claims description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims description 3
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 3
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000013598 vector Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229940063656 aluminum chloride Drugs 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002122 magnetic nanoparticle Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical group [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 1
- 239000010747 number 6 fuel oil Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention relates to a method for manufacturing a catalyst carrier for tail gas of a marine diesel engine, which is characterized in that a mixed solution of magnetic iron oxide particles and aluminum chloride is placed in a magnetic field environment to prepare a gel, the magnetic iron oxide particles form orderly and controllable connection under the magnetic field environment, the magnetic iron oxide particles are mutually crosslinked, and a honeycomb-shaped skeleton structure is formed in the mixed solution and the gel. The manufacturing method can directly form a binary non-mixed structure in a gel process, and in the structure, the iron oxide and the alumina are not mixed and mixed with each other; compared with the existing carrier, the binary non-mixed structure greatly increases the specific surface area, when the catalyst is coated on the carrier, a very high specific surface area can be formed, compared with the existing honeycomb catalyst, the specific surface area can be increased by 30-50%, and NO is increased X The conversion of (2).
Description
Technical Field
The invention relates to the field of tail gas treatment of marine power units, in particular to a method for manufacturing a catalyst carrier for tail gas of a marine diesel engine.
Background
With the increasing development of globalization and international trade, goods are transported more and more in various countries and regions around the world, and the demand for goods transportation is also increased. The ship transportation has become the most important transportation mode in international trade transportation by virtue of the advantages of large transportation volume, long transportation distance and low cost, and plays a very important role in the goods transportation of international trade.
At present, the marine engine mainly includes a gas turbine, a steam turbine, and a diesel engine. The diesel engine has the advantages of high thermal efficiency, good economy, easy starting, strong adaptability to various ships and the like, so that the diesel engine is mainly selected as the engine in the current commercial ships. In international logistics transportation, a commercial ship mainly uses a diesel engine as a power source, and due to the large carrying capacity and long sailing distance of the ship, a large amount of fuel oil needs to be consumed in the transportation process, and according to statistics, the consumption of the bunker fuel oil accounts for more than 35% of the total consumption of global fuel oil. While the diesel engineWhen fuel is consumed, a large amount of pollutants including particulate matter, CO and NO are generated X 、SO 2 HC, NO, etc., wherein the particulate matter not only causes severe haze weather, but also causes damage to human health X Can generate photochemical smog with strong toxicity under proper conditions, NO X And SO 2 The carbon dioxide is easy to dissolve in water to form acid rain, so that the ecological environment is seriously damaged, and CO has toxic effect on human bodies; the discharged pollutants cause great pollution and damage to the environment and people. According to statistics, the combustion of the marine diesel engines worldwide discharges NO to the atmosphere every year X About 650 million tons, SO 2 About 600 million tons, therefore, the exhaust emission of the marine diesel engine is treated, and the emission of pollutants is urgently reduced.
At present, for NO in exhaust gas X The current mature emission treatment is selective catalytic reduction SCR, which works on the principle that ammonia or urea is used as a reducing agent to selectively react with NO in exhaust gas at a certain temperature under the action of a catalyst X Reacting to produce harmless N 2 And water, thereby achieving the purpose of reducing NO in the tail gas of the diesel engine X The purpose of content. This technique enables NO X The emission amount of the diesel engine is reduced by more than 90%, and the structure of the diesel engine does not need to be changed, so the diesel engine is widely applied.
The catalysts of current marine SCR systems are mainly metal oxides coated on a carrier, which has a main structural form of honeycomb, and a few corrugated plates. The specific surface area of the carrier is increased through the honeycomb carrier, namely the contact area of the catalyst and the waste gas is increased, so that the catalyst is fully contacted with the waste gas, and the conversion rate is improved; the larger the specific surface area is, the larger the contact area of the catalyst with the exhaust gas is, and the higher the conversion rate is. However, how to further increase the specific surface area of the catalyst support is a problem that those skilled in the art have sought and need to solve.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for manufacturing a catalyst carrier for marine diesel engine tail gas, which is characterized in that a binary non-mixed aerogel material structure of iron oxide and alumina is prepared by a sol-gel method, the iron oxide is used as a backbone structure, alumina supports are formed in pores between iron oxide backbones, and then the binary non-mixed aerogel structure is formed.
The method for manufacturing the catalyst carrier for the tail gas of the marine diesel engine comprises the following steps:
step one, preparing a solvent containing aluminum salt;
step two, adding magnetic iron oxide particles into the solvent obtained in the step one, and uniformly stirring to obtain a mixed solution of aluminum salt and magnetic iron oxide particles;
step three, placing the mixed solution obtained in the step two in a magnetic field environment, adding an epoxide into the mixed solution obtained in the step two at the temperature of 0-4 ℃, and stirring for 3-5 minutes;
step four, then placing the mixture into a thermostat with the temperature of 40-55 ℃ in a magnetic field environment and standing for 2-5 days to form gel;
step five, adding absolute ethyl alcohol after gel is formed in the step four, sealing in a liquid mode, and aging;
step six, keeping the wet gel aged in the step five in a magnetic field environment for drying to obtain aerogel;
step seven, pre-burning the dried aerogel at 650-950 ℃, and preserving heat for 0.5-3 hours;
and step eight, roasting the pre-sintered aerogel obtained in the step seven at 1500 ℃ for 5-10 hours to obtain binary non-mixed aerogel of iron oxide and aluminum oxide, and processing the binary non-mixed aerogel of iron oxide and aluminum oxide to obtain the catalyst carrier.
Further, the solvent containing aluminum salt is prepared in the step one by dissolving soluble aluminum salt in water and absolute ethyl alcohol, wherein the soluble aluminum salt is aluminum chloride hexahydrate, aluminum nitrate nonahydrate or aluminum sulfate octadecahydrate.
Further, the iron oxide particles in the second step are iron oxide particles or ferroferric oxide particles, and the diameter range of the iron oxide particles is 20-100nm. The ferric oxide particles or ferroferric oxide particles are prepared by a solvent method, a coprecipitation method or a hydrothermal method.
Further, the epoxide in step three is ethylene oxide, propylene oxide or epichlorohydrin.
Further, the third step, the fourth step, the fifth step and the sixth step are all carried out in the same magnetic field environment. The magnetic field environment is a magnetic field with uniform strength and parallel distribution of magnetic induction lines, or a magnetic field with non-uniform strength and parallel distribution of magnetic induction lines, or a composite magnetic field formed by superposing a transverse magnetic field and a longitudinal magnetic field.
Further, the drying in the sixth step is vacuum drying, normal pressure drying or supercritical drying.
The implementation of the invention has the following beneficial effects: the gel is prepared by placing the mixed solution of the magnetic iron oxide particles and the aluminum chloride in a magnetic field environment, the magnetic iron oxide particles are orderly and controllably connected with each other in the magnetic field environment, the magnetic iron oxide particles are mutually connected, and a honeycomb-shaped skeleton structure is formed in the mixed solution and the gel. The aluminum chloride is not influenced by a magnetic field, is distributed in the framework structure formed by the iron oxide particles, and forms a fixed alumina bracket or an irregular attachment structure on the framework in the subsequent process, and the alumina bracket or the attachment structure is fixedly dispersed in pores formed by the framework structure formed by the iron oxide particles, so that a binary non-mixed structure taking the iron oxide as the framework and the alumina as the framework is formed. Compared with the existing catalyst carrier, the preparation method can directly form a binary non-mixed structure in a gel process, and in the structure, the iron oxide and the alumina are not mixed or mixed with each other; compared with the existing carrier, the binary non-mixed structure greatly increases the specific surface area, when the catalyst is coated on the carrier, a very high specific surface area can be formed, compared with the existing honeycomb catalyst, the specific surface area can be increased by 30-50%, and NO is increased X The conversion of (2).
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments or the prior art descriptions will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts.
Fig. 1 is a flowchart of a method for manufacturing a catalyst carrier for marine diesel engine exhaust gas according to the present invention.
Fig. 2 is a magnetic field environment of the present invention.
Fig. 3 is a microscopic view of a catalyst carrier obtained by the method for manufacturing a catalyst carrier for exhaust gas of marine diesel engines according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
The method for manufacturing the catalyst carrier for the tail gas of the marine diesel engine comprises the following steps:
step one, preparing an aluminum salt solvent.
Preparing an aluminum salt solvent, and using soluble aluminum salt, wherein the soluble aluminum salt is aluminum chloride hexahydrate, aluminum nitrate nonahydrate or aluminum sulfate octadecahydrate. Distilled water and absolute ethyl alcohol are taken firstly to prepare a solvent, then soluble aluminum salt is added into the solvent, and the mixture is stirred for a period of time to fully dissolve the aluminum salt, so as to obtain the aluminum salt solvent.
And step two, adding the magnetic iron oxide particles into the solution obtained in the step one, and uniformly stirring to obtain a mixed solution of aluminum salt and magnetic iron oxide particles.
The magnetic iron oxide particles are magnetic iron oxide nanoparticles, the diameter of the magnetic nanoparticles is generally below 100nm, and the magnetic nanoparticles have outstanding superparamagnetic properties, i.e. the particles can be rapidly magnetized under the action of a magnetic field, and have no remanence after the external magnetic field is removed. The iron oxide is gamma-iron oxide or ferroferric oxide, and the gamma-iron oxide particles and the ferroferric oxide particles have magnetism, so that under the action of a magnetic field, the like poles of adjacent particles repel and the opposite poles attract under the magnetization condition, and the adjacent particles are mutually crosslinked through magnetic force.
The magnetic iron oxide particles have small sizes and are prepared by a solvent method, a coprecipitation method or a hydrothermal method.
Adding the obtained magnetic iron oxide particles into an aluminum salt solvent, and fully stirring for 5-8min to fully and uniformly disperse the magnetic iron oxide particles in the aluminum salt solvent to obtain a mixed solution.
And step three, after the aluminum salt and magnetic iron oxide particle mixed solution obtained in the step two is obtained, the mixed solution is placed in a magnetic field environment, the magnetic iron oxide particles in the mixed solution begin to generate magnetic force action under the action of a magnetic field, the magnetic iron oxide particles in the mixed solution repel each other in the same polarity and attract each other in the opposite polarity, and the adjacent iron oxide particles begin to be connected with each other under the action of the magnetic force to form a three-dimensional honeycomb structure. And the aluminum salt in the mixed solution is not influenced by an external magnetic field because of no magnetism, and the aluminum salt is dispersed in the pores of the honeycomb structure formed by the iron oxide particles in the mixed solution.
And then reducing the temperature of the mixed solution to 0-4 ℃ in the magnetic field environment, adding the epoxide into the mixed solution, fully and uniformly stirring the mixture for 3-5 minutes. Because of stirring under the magnetic field environment, the stirring device can disturb the honeycomb structure formed before, but after the full stirring is finished, the iron oxide particles in the mixed solution still form a three-dimensional honeycomb structure.
Wherein the epoxide is ethylene oxide, propylene oxide or epichlorohydrin.
For the magnetic field environment, the magnetic field intensity is weaker, and the intensity is preferably selected so as not to enable the magnetic iron oxide particles in the mixed solution to form strong and obvious arrangement. The magnetic field strength is preferably 0.01 to 0.38 tesla.
The magnetic field can be a magnetic field with uniform strength and parallel distribution of magnetic induction lines, or a magnetic field with nonuniform strength and parallel distribution of magnetic induction lines, or a composite magnetic field formed by superposing a transverse magnetic field and a longitudinal magnetic field.
When a uniform-strength magnetic field with parallel magnetic induction lines is selected, the magnetic iron oxide particles in the mixed solution can be approximately arranged along the same direction, and the overall directions of pores in the formed three-dimensional honeycomb structure are approximately the same. The catalyst carrier made of the three-dimensional honeycomb structure formed in the way has the advantage of low through-flow resistance.
The magnetic field can also be formed by superposing a transverse magnetic field and a longitudinal magnetic field, wherein the transverse magnetic field and/or the longitudinal magnetic field can be a single continuous magnetic field, and more preferably a discrete discontinuous magnetic field. The included angle between the longitudinal magnetic field and the transverse magnetic field is 60-300 degrees. For example, a longitudinal magnetic field with adjustable strength is superposed in the orthogonal direction of a transverse magnetic field, namely the longitudinal direction, at the moment, in a composite magnetic field formed by superposing the transverse magnetic field and the longitudinal magnetic field, the direction and the strength of a magnetic induction line in a specific position are vectors synthesized after the magnetic induction line vector of the transverse magnetic field and the magnetic induction line vector of the longitudinal magnetic field are superposed, and the direction and the strength of the magnetic induction line of the composite magnetic field at the point are determined by the strength of the transverse magnetic field and the longitudinal magnetic field. Therefore, the magnetic field direction and the strength of the composite magnetic field can be adjusted by adjusting the strength of the longitudinal magnetic field, and the approximate trend of the framework and the pores in the honeycomb structure can be further adjusted. More preferably, the longitudinal magnetic field intersecting the transverse magnetic field is a discontinuous magnetic field discretely distributed in the transverse direction, thereby forming a plurality of composite magnetic fields, which are formed at intervals from the transverse magnetic field. Different composite magnetic fields are generated by adjusting the strength of each longitudinal magnetic field, so that a complex honeycomb structure with multiple trends is formed. When the tail gas flows through the catalyst carrier made of the honeycomb structure with complex trend, the flow path is prolonged, and NO in the waste gas is generated X The reaction time is longer, and the conversion efficiency is higher. Through adjusting the strength and the direction of each discrete longitudinal magnetic field, a plurality of complex composite magnetic field structures are constructed, and then honeycomb structures with various complex configurations are constructed, so that various requirements are met.
The magnetic field can also be directly selected from a magnetic field with non-uniform strength and parallel distribution of magnetic induction lines.
The magnetic field can be generated by a permanent magnet, or an electromagnetic field, or by the superposition and composition of the permanent magnet and the electromagnetic field.
And step four, after the mixed solution with the primarily formed honeycomb structure is obtained in the step three, placing the mixed solution into a constant temperature box with the temperature of 40-55 ℃ in a magnetic field environment and standing for 2-5 days to form gel. During this time, the three-dimensional honeycomb structure formed by the magnetic iron oxide particles is maintained due to the magnetic field environment.
And step five, adding absolute ethyl alcohol into the gel formed in the step four, sealing the gel in a liquid, putting the gel into a thermostat at 45 ℃, and aging the gel for 3 to 5 days.
And step six, keeping the wet gel aged in the step five in a magnetic field environment for drying to obtain the aerogel. Wherein, the drying of the wet gel is vacuum drying, normal pressure drying or supercritical drying. The drying process is also carried out in a magnetic field environment, preferably the same as the previous magnetic field environment, to maintain the stability of the honeycomb structure.
And seventhly, pre-burning the dried aerogel at 650-950 ℃, and preserving heat for 0.5-3 hours.
Through the pre-burning step, the solid honeycomb structure formed by the iron oxide particles is firstly firmly shaped and strengthened. Secondly, the aluminum salt particles in the three-dimensional honeycomb structure are reacted to form alumina particles through pre-sintering, and the alumina particles are connected and consolidated through the pre-sintering to form a primary alumina bracket in the pores of the honeycomb structure. Through the pre-burning step, the framework and the bracket in the formed honeycomb structure can be more compact, the internal pores are reduced, and the strength is improved.
And step eight, roasting the pre-sintered aerogel obtained in the step seven at 1500 ℃ for 5-10 hours, finally forming the pre-sintered honeycomb-structure aerogel obtained in the step seven to obtain the binary non-mixed aerogel of the iron oxide and the aluminum oxide, and processing the binary non-mixed aerogel of the iron oxide and the aluminum oxide to obtain the catalyst carrier.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (10)
1. A method for manufacturing a catalyst carrier for marine diesel exhaust, comprising:
step one, preparing a solvent containing aluminum salt;
step two, adding magnetic iron oxide particles into the solvent obtained in the step one, and uniformly stirring to obtain a mixed solution of aluminum salt and magnetic iron oxide particles;
step three, placing the mixed solution obtained in the step two in a magnetic field environment, adding an epoxide into the mixed solution obtained in the step two at the temperature of 0-4 ℃, and stirring for 3-5 minutes to uniformly mix the mixed solution;
step four, then placing the mixture into a thermostat with the temperature of 40-55 ℃ in a magnetic field environment and standing for 2-5 days to form gel;
after gel is formed in the step four, adding absolute ethyl alcohol into the gel in a magnetic field environment for liquid sealing, and aging;
step six, keeping the wet gel aged in the step five under a magnetic field environment for drying to obtain aerogel;
step seven, pre-burning the dried aerogel at 650-950 ℃, and preserving heat for 0.5-3 hours;
and step eight, roasting the pre-sintered aerogel obtained in the step seven at 1500 ℃ for 5-10 hours to obtain iron oxide and aluminum oxide binary non-mixed aerogel, and processing the iron oxide and aluminum oxide binary non-mixed aerogel to obtain the catalyst carrier.
2. The process according to claim 1, wherein the aluminum salt in the first step is aluminum chloride hexahydrate, aluminum nitrate nonahydrate or aluminum sulfate octadecahydrate.
3. The method according to claim 1, wherein the magnetic iron oxide particles in step two are iron oxide particles or ferroferric oxide particles, and the diameter of the particles is 20-100nm.
4. The manufacturing method according to claim 3, wherein the iron oxide fine particles are γ -iron oxide fine particles.
5. The process according to claim 1, wherein the epoxide in the third step is ethylene oxide, propylene oxide or epichlorohydrin.
6. The method of claim 1, wherein the magnetic field environment in steps three, four, five, and six is the same magnetic field environment.
7. The manufacturing method according to claim 6, wherein the magnetic field environment is a uniform magnetic field with parallel magnetic induction lines, or a non-uniform magnetic field with parallel magnetic induction lines, or a composite magnetic field formed by superposing a transverse magnetic field and a longitudinal magnetic field.
8. The method according to claim 7, wherein the longitudinal magnetic field is a continuous uniform magnetic field, and the angle between the longitudinal magnetic field and the transverse magnetic field is 60-300 °.
9. The method according to claim 7, wherein the longitudinal magnetic fields are discontinuous magnetic fields, the intensity of each longitudinal magnetic field is arbitrarily selected from a range of 0.01-0.38 Tesla, and the included angle between the direction of each longitudinal magnetic field and the direction of the transverse magnetic field is arbitrarily selected from a range of 60-300 °.
10. The production method according to claim 1, wherein the drying in the sixth step is vacuum drying, atmospheric drying or supercritical drying.
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