CN116099569A - Catalyst for purifying tail gas of ammonia internal combustion engine and preparation method and application thereof - Google Patents

Catalyst for purifying tail gas of ammonia internal combustion engine and preparation method and application thereof Download PDF

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Publication number
CN116099569A
CN116099569A CN202310137998.9A CN202310137998A CN116099569A CN 116099569 A CN116099569 A CN 116099569A CN 202310137998 A CN202310137998 A CN 202310137998A CN 116099569 A CN116099569 A CN 116099569A
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copper
molecular sieve
ammonia
ruthenium
internal combustion
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贺泓
徐光艳
安琦
***
余运波
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Research Center for Eco Environmental Sciences of CAS
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Research Center for Eco Environmental Sciences of CAS
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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
    • 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
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/763—CHA-type, e.g. Chabazite, LZ-218
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material

Abstract

The invention relates to a catalyst for purifying tail gas of an ammonia internal combustion engine, and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, mixing an ammonia type molecular sieve and a copper salt solution, performing solid-liquid separation and first roasting to obtain a copper-loaded molecular sieve; s2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and sequentially carrying out ruthenium salt treatment, evaporation and second roasting to obtain the catalyst for purifying the tail gas of the ammonia internal combustion engine. According to the preparation method provided by the invention, the active components ruthenium and copper are introduced in a specific preparation process, ruthenium in the obtained catalyst mainly exists in an oxidation state, and copper mainly exists in an ionic state, so that the efficient ammonia oxidation reaction under the gas environment of nitrogen oxides, water vapor and the like is realized by utilizing the cooperation of the ruthenium in the oxidation state and the copper in the ionic state, and the purification requirement of tail gas of an ammonia internal combustion engine under actual conditions is met.

Description

Catalyst for purifying tail gas of ammonia internal combustion engine and preparation method and application thereof
Technical Field
The invention relates to the field of tail gas purification, in particular to a catalyst for purifying tail gas of an ammonia internal combustion engine, a preparation method and application thereof.
Background
At present, ammonia is taken as an ideal energy storage substance, the molecule of the ammonia does not contain carbon element, the complete combustion product only comprises water and nitrogen, and compared with most gas fuels, the ammonia has the characteristic of being easily compressed into a liquid state, so that the ammonia is convenient to store and transport, and the ammonia has the potential of becoming an alternative fuel for an internal combustion engine.
As CN115095455a discloses an ammonia combustion internal combustion engine, through setting up internal combustion engine, the intake pipe, the filter screen, the swivel becket, the clearance board, a groove, a spring, the guide pillar, extend the box, no. two springs, the counter weight stick, through setting up the filter screen in the intake pipe, thereby it is isolated impurity, prevent that impurity from entering into the combustion chamber of internal combustion engine through the intake pipe inside, and provide kinetic energy for the clearance board through the energy that intake pipe self rocked, the clearance board carries out the segmentation clearance to the mesh of filter screen, guarantee again can not block up the filter screen in the clearance, thereby reduce the filter screen that blocks up and lead to the unable timely intake pipe of follow internal combustion engine of air to enter into the combustion chamber of internal combustion engine, thereby cause the probability that this problem of power decline of internal combustion engine takes place.
CN115234391a discloses a constant pressure combustion control method and device for an ammonia internal combustion engine and the internal combustion engine, and relates to the field of power and energy engineering. Aiming at the problems of high octane number of ammonia fuel, serious high burst pressure during direct injection compression ignition in an ammonia fuel cylinder, great requirements on mechanical strength and thermal load of an internal combustion engine and influence on efficiency and reliability of the internal combustion engine in the prior art, the invention provides a method for controlling the burst pressure of ammonia combustion and carrying out pulse injection of the ammonia for the direct injection and the constant pressure combustion in the ammonia internal combustion engine, which comprises the following steps: the method for controlling the constant pressure combustion of the internal combustion engine comprises the following steps: step 1: determining a highest operating pressure of an internal combustion engine based on a characteristic of the internal combustion engine; step 2: determining a first fuel injection parameter and an optimal injection number according to the highest operating pressure; step 3: after the internal pressure of the internal combustion engine drops, fuel injection is performed; and 4, repeating the step 3 until the optimal injection times are reached. Is suitable for being applied to the research and implementation of ammonia fuel compression ignition.
However, part of fuel ammonia is still not fully combusted in the combustion process of the ammonia internal combustion engine, meanwhile, nitrogen oxides and water vapor are formed in the combustion process of the ammonia, and the nitrogen oxides formed in the combustion process can cause the performance of the existing ammonia decomposition catalyst to be reduced in the actual environment, secondary pollutants nitrogen dioxide and nitrous oxide are easy to be generated, so that the tail gas cannot be effectively purified.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a catalyst for purifying tail gas of an ammonia internal combustion engine, and a preparation method and application thereof, so as to solve the problem of poor tail gas purifying effect when a small amount of nitrogen oxides exist in tail gas of the ammonia internal combustion engine.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a catalyst for purifying an exhaust gas of an ammonia internal combustion engine, the method comprising:
s1, mixing an ammonia type molecular sieve and a copper salt solution, performing solid-liquid separation and first roasting to obtain a copper-loaded molecular sieve;
s2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and sequentially carrying out ruthenium salt treatment, evaporation and second roasting to obtain the catalyst for purifying the tail gas of the ammonia internal combustion engine.
According to the preparation method provided by the invention, active components of ruthenium and copper are introduced in a specific preparation process, and the low-temperature activity and nitrogen selectivity of the ammoxidation reaction of the catalyst are improved by utilizing the synergistic effect of metals. Ruthenium in the catalyst mainly exists in an oxidation state, and copper mainly exists in an ionic state, so that the efficient ammonia oxidation reaction under the gas environment of nitrogen oxides, water vapor and the like is realized by utilizing the coordination of the ruthenium in the oxidation state and the copper in the ionic state, and the purification requirement of tail gas of an ammonia internal combustion engine under the actual condition is met.
In the present invention, in order to ensure the loading of the active material in the catalyst, the steps S1 and S2 may be performed a plurality of times.
In the invention, a drying process can be added between solid-liquid separation and first roasting and between evaporation and second roasting to sufficiently remove residual materials such as solvent or moisture.
As a preferred embodiment of the present invention, the ammonia-type molecular sieve comprises 1 or a combination of at least 2 of ZSM-5 molecular sieve, SSZ-13 molecular sieve or Y molecular sieve.
Preferably, the copper salt used for the copper salt solution of the configuring step (1) comprises 1 or a combination of at least 2 of copper chloride, copper sulfate, copper nitrate or copper acetate, preferably copper nitrate.
Preferably, the concentration of copper element in the copper salt solution is 3.2-128g/L, for example, it may be 3.2g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 12g/L, 14g/L, 16g/L, 18g/L, 20g/L, 22g/L, 24g/L, 26g/L, 28g/L, 30g/L, 32g/L, 34g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L, 48g/L, 50g/L, 52g/L, 54g/L, 56g/L, 58g/L, 60g/L, 62 g/L64 g/L, 66g/L, 68g/L, 70 g/L, 72g/L, 74g/L, 76g/L, 78g/L, 80g/L, 82g/L, 84g/L, 86g/L, 88g/L, 90g/L, 92g/L, 94g/L, 96g/L, 98g/L, 100g/L, 102g/L, 104g/L, 106g/L, 108g/L, 110g/L, 112g/L, 114g/L, 116g/L, 118g/L, 120g/L, 122g/L, 124g/L, 126g/L, 128g/L, etc., but are not limited to, the recited values, and other non-recited values within this range are equally applicable.
Preferably, the solid to liquid ratio g/mL of the ammonia-type molecular sieve and copper salt solution is 1 (10-150), which may be, for example, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95, 1:100, 1:105, 1:110, 1:115, 1:120, 1:125, 1:130, 1:135, 1:140, 1:145, or 1:150, etc., but is not limited to the recited values, as other non-recited values within this range are equally applicable.
As a preferable technical scheme of the invention, the mixing time of the ammonia type molecular sieve and the copper salt solution is 5-8h, for example, 5h, 5.1h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h, 5.8h, 5.9h, 6h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h, 7h, 7.1h, 7.2h, 7.3h, 7.4h, 7.5h, 7.6h, 7.7h, 7.8h, 7.9h or 8h, etc., but the ammonia type molecular sieve is not limited to the listed values, and other values not listed in the range are equally applicable.
In a preferred embodiment of the present invention, the first firing temperature may be 500 to 700 ℃, for example, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the time of the first calcination is 5 to 9 hours, for example, 5 hours, 5.1 hours, 5.2 hours, 5.3 hours, 5.4 hours, 5.5 hours, 5.6 hours, 5.7 hours, 5.8 hours, 5.9 hours, 6 hours, 6.1 hours, 6.2 hours, 6.3 hours, 6.4 hours, 6.5 hours, 6.6 hours, 6.7 hours, 6.8 hours, 6.9 hours, 7 hours, 7.1 hours, 7.2 hours, 7.3 hours, 7.4 hours, 7.5 hours, 7.6 hours, 7.7 hours, 7.8 hours, 7.9 hours, 8 hours, 8.1 hours, 8.2 hours, 8.3 hours, 8.4 hours, 8.5 hours, 8.6 hours, 8.8 hours, 8.9 hours, or 9 hours, etc., but the present invention is not limited to the values mentioned above, and other values not mentioned in this range are equally applicable.
As a preferred embodiment of the present invention, the solvent comprises water and/or ethanol.
Preferably, the copper-loaded molecular sieve and solvent are mixed for a period of time ranging from 1 to 4 hours, such as 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h or 4h, but are not limited to the recited values, as other values not recited within this range are equally applicable.
As a preferable technical scheme of the invention, the ruthenium salt treatment is to add ruthenium salt into a material obtained after the copper-carrying molecular sieve and the solvent are mixed.
Preferably, the ruthenium salt used in the ruthenium salt treatment comprises 1 or a combination of at least 2 of ruthenium trichloride, ruthenium trinitronitrosyl or ruthenium acetate, preferably ruthenium trinitrosyl.
Preferably, the mass ratio of the copper-bearing molecular sieve in the ruthenium salt treatment to the ruthenium element in the ruthenium salt used is 1 (0.005-0.05), which may be, for example, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01, 1:0.012, 1:0.014, 1:0.016, 1:0.018, 1:0.02, 1:0.022, 1:0.024, 1:0.026, 1:0.028, 1:0.03, 1:0.032, 1:0.034, 1:0.036, 1:0.038, 1:0.04, 1:0.042, 1:0.044, 1:0.046, 1:0.048 or 1:0.05, etc., although other non-enumerated values within this range are equally applicable
As a preferred technical scheme of the invention, the evaporation comprises water bath rotary evaporation;
the evaporating temperature is preferably 50 to 80 ℃, and may be, for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, or 80 ℃, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The second firing temperature is preferably 400 to 700 ℃, and may be 400 to 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, or the like, for example, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the second calcination time is 4-8h, for example, 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h, 5h, 5.1h, 5.2h, 5.3h, 5.4h, 5.5h, 5.6h, 5.7h, 5.8h, 5.9h, 6h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h, 7h, 7.1h, 7.2h, 7.3h, 7.4h, 7.5h, 7.6h, 7.8h, 7.9h or 8h, etc., but not limited to the values recited herein, and other values not recited herein are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
s1, mixing an ammonia type molecular sieve and a copper salt solution, performing solid-liquid separation and first roasting to obtain a copper-loaded molecular sieve;
s2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and sequentially carrying out ruthenium salt treatment, evaporation and second roasting to obtain a catalyst for purifying the tail gas of the ammonia internal combustion engine;
the ammonia type molecular sieve in S1 comprises 1 or at least 2 of ZSM-5 molecular sieve, SSZ-13 molecular sieve or Y molecular sieve; the copper salt used in the copper salt solution comprises 1 or a combination of at least 2 of copper chloride, copper sulfate, copper nitrate or copper acetate; the concentration of copper element in the copper salt solution is 3.2-128g/L; the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and copper salt solution is 1 (10-150); the mixing time of the ammonia type molecular sieve and the copper salt solution is 5-8h; the temperature of the first roasting is 500-700 ℃; the first roasting time is 5-9h;
the solvent in S2 comprises water and/or ethanol; the mixing time of the copper-carrying molecular sieve and the solvent is 1-4 hours; the ruthenium salt treatment is to add ruthenium salt into a material obtained after the copper-carrying molecular sieve and the solvent are mixed; the ruthenium salt used in the ruthenium salt treatment comprises 1 or a combination of at least 2 of ruthenium trichloride, ruthenium trinitronitrosyl or ruthenium acetate; the mass ratio of the copper-carrying molecular sieve in the ruthenium salt treatment to the ruthenium element in the ruthenium salt is 1 (0.005-0.05); the evaporation comprises water bath rotary evaporation; the evaporating temperature is 50-80 ℃; the temperature of the second roasting is 400-700 ℃; the second roasting time is 4-8h.
In the present invention, the solvent used in preparing the solution is a solvent commonly used in the art, and may be water and/or ethanol, etc.
In a second aspect, the invention provides a catalyst for purifying exhaust gas of an ammonia internal combustion engine, which is prepared by the preparation method according to the first aspect, and comprises the following active components in percentage by mass: 0.5-5% of ruthenium, 2-5% of copper and the balance of molecular sieve carrier.
In the present invention, the ruthenium as an active component of the catalyst for purifying exhaust gas of an ammonia internal combustion engine is 0.5 to 5% by mass, and for example, may be 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8% or 5% by mass, etc., but is not limited to the recited values, and other non-recited values are equally applicable in the range.
In the present invention, the amount of copper as an active component of the catalyst for purifying exhaust gas of an ammonia internal combustion engine is 2 to 5% by mass, and may be, for example, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9% or 5%, etc., but the present invention is not limited to the values recited above, and other values not recited in the range are equally applicable.
In a third aspect, the present invention provides the use of the catalyst for purifying exhaust gas of an ammonia internal combustion engine obtained by the production method according to the first aspect, which comprises catalytic purification of exhaust gas formed during operation of the ammonia internal combustion engine using the molecular sieve catalyst.
The catalytic purification temperature may be 200 to 500 ℃, for example, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The water content in the exhaust gas of the ammonia internal combustion engine is 5-15% by volume, for example, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% or 15%, etc., but not limited to the recited values, and other non-recited values in the range are equally applicable.
The ammonia gas in the exhaust gas formed by the ammonia internal combustion engine has a concentration of 500 to 2000ppm, for example, 500ppm, 550ppm, 600ppm, 650ppm, 700ppm, 750ppm, 800ppm, 850ppm, 900ppm, 950ppm, 1000ppm, 1050ppm, 1100ppm, 1150ppm, 1200ppm, 1250ppm, 1300ppm, 1350ppm, 1400ppm, 1450ppm, 1500ppm, 1550ppm, 1600ppm, 1650ppm, 1700ppm, 1750ppm, 1800ppm, 1850ppm, 1900ppm, 1950ppm, 2000ppm, etc., but the present invention is not limited to the values recited, and other values not recited in the present invention are equally applicable.
The concentration of nitric oxide in the exhaust gas formed by the ammonia internal combustion engine is 100-500ppm, for example, 100ppm, 120ppm, 140ppm, 160ppm, 180ppm, 200ppm, 220ppm, 240ppm, 260ppm, 280ppm, 300ppm, 320ppm, 340ppm, 360ppm, 380ppm, 400ppm, 420ppm, 440ppm, 460ppm, 480ppm or 500ppm, etc., but not limited to the recited values, and other values not recited in this range are equally applicable.
In the invention, the total flow of the gas in purification can be 400-600mL/min, and the airspeed is 100000-300000h -1 。
Compared with the prior art, the invention has the following beneficial effects:
(1) The ammonia oxidation catalyst has higher activity in the range of 200-500 ℃ and in the presence of 5-15% of water vapor, and can meet the requirements of an ammonia internal combustion engine on catalyst tail gas purification under the conditions of a small amount of nitrogen oxides and water vapor. Noble metal ruthenium has excellent oxidizing ability, and is distributed on a molecular sieve carrier in a form of small nano particles to be matched with ionic copper, so that ammonia can be completely oxidized in the presence of nitrogen oxides.
(2) Under the condition that nitrogen oxides exist in tail gas, the ammonia oxidation catalyst still has higher nitrogen selectivity (91-99%) within the range of 200-500 ℃, meets the requirement of purifying gas in an ammonia internal combustion engine, and the active metal copper exists in the catalyst in a highly dispersed ion form to be matched with ruthenium in an oxidation state, so that by-product nitrogen oxides and nitrogen monoxide in the tail gas are selectively reduced into nitrogen, and the nitrogen selectivity is improved.
Drawings
FIG. 1 is a graph showing the ammonia conversion and nitrogen selectivity of the ammoxidation reaction in practical example 1 of the present invention.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The embodiment provides a catalyst for purifying tail gas of an ammonia internal combustion engine, wherein the molecular sieve catalyst comprises the following active components in percentage by mass: ruthenium 2% and copper 4%, the balance being molecular sieve carrier.
The preparation method comprises the following steps:
s1, mixing an ammonia type molecular sieve and a copper salt solution, and then sequentially carrying out solid-liquid separation, drying and first roasting to obtain a copper-carrying molecular sieve;
preparing a copper salt used by the copper salt solution in the step S1 to be copper nitrate; the ammonia type molecular sieve is an SSZ-13 molecular sieve; the molar concentration of copper element in the copper salt solution is 6.4g/L; the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and copper salt solution is 1:100; the temperature of stirring is 60 ℃ and the time is 6 hours; the temperature of the first roasting is 600 ℃ and the time is 6 hours;
in this example, S1 was performed 2 times to ensure that the copper loading could reach 4%.
S2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and then sequentially carrying out ruthenium salt treatment, evaporation, drying and second roasting to obtain a catalyst for purifying the tail gas of the ammonia internal combustion engine;
s2, the solvent is deionized water; the temperature of the mixing is 25 ℃ and the time is 0.5h; the ruthenium salt treatment is to add ruthenium salt into the materials obtained by mixing, wherein the ruthenium salt used in the ruthenium salt treatment is trinitronitrosyl, and the mass ratio of the copper-carrying molecular sieve in the ruthenium salt treatment to ruthenium element in the ruthenium salt is 1:0.02; the evaporation comprises water bath rotary evaporation, and the temperature is 60 ℃; the temperature of the second roasting is 550 ℃ and the time is 4 hours.
Example 2
The embodiment provides a catalyst for purifying tail gas of an ammonia internal combustion engine, wherein the molecular sieve catalyst comprises the following active components in percentage by mass: ruthenium 2.5% and copper 4%, the balance being molecular sieve support.
The preparation method comprises the following steps:
s1, mixing an ammonia type molecular sieve and a copper salt solution, and then sequentially carrying out solid-liquid separation, drying and first roasting to obtain a copper-carrying molecular sieve;
preparing copper salt used in the copper salt solution in the step S1 to be copper nitrate; the ammonia type molecular sieve is an SSZ-13 molecular sieve; the molar concentration of copper element in the copper salt solution is 3.2g/L; the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and copper salt solution is 1:100; the temperature of the first mixing and stirring is 60 ℃ and the time is 6 hours; the temperature of the first roasting is 600 ℃ and the time is 5 hours;
s2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and then sequentially carrying out ruthenium salt treatment, evaporation, drying and second roasting to obtain a catalyst for purifying the tail gas of the ammonia internal combustion engine;
s2, the solvent is deionized water; the temperature of the second mixing and stirring is 25 ℃ and the time is 0.5h; the ruthenium salt treatment is to add ruthenium salt into the materials obtained by mixing, wherein the ruthenium salt used in the ruthenium salt treatment is trinitronitrosylruthenium, and the mass ratio of the copper-carrying molecular sieve in the ruthenium salt treatment to the ruthenium element in the used ruthenium salt is 1:0.025; the evaporation is water bath rotary evaporation, and the temperature is 60 ℃; the temperature of the second roasting is 550 ℃ and the time is 4 hours.
Example 3
The embodiment provides a catalyst for purifying tail gas of an ammonia internal combustion engine, wherein the molecular sieve catalyst comprises the following active components in percentage by mass: 1.0% of ruthenium and 4% of copper, and the balance of molecular sieve carrier.
The preparation method comprises the following steps:
s1, mixing an ammonia type molecular sieve and a copper salt solution, and then sequentially carrying out solid-liquid separation, drying and first roasting to obtain a copper-loaded molecular sieve;
preparing a copper salt used by the copper salt solution in the step S1 to be copper nitrate; the ammonia type molecular sieve is an SSZ-13 molecular sieve; the concentration of copper element in the copper salt solution is 6.4/L; the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and copper salt solution is 1:100; the temperature of the mixing is 60 ℃ and the time is 6 hours; the temperature of the first roasting is 600 ℃ and the time is 5 hours;
s2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and then sequentially carrying out ruthenium salt treatment, evaporation, drying and second roasting to obtain a catalyst for purifying the tail gas of the ammonia internal combustion engine;
s2, the solvent is deionized water; the temperature of the mixing is 25 ℃ and the time is 0.5h; the ruthenium salt treatment is to add ruthenium salt into the materials obtained by mixing, wherein the ruthenium salt used in the ruthenium salt treatment is trinitronitrosylruthenium, and the mass ratio of the copper-loaded molecular sieve in the ruthenium salt treatment to the ruthenium element in the ruthenium salt used is 1:0.010; the evaporation is water bath rotary evaporation, and the temperature is 60 ℃; the temperature of the second roasting is 550 ℃ and the time is 8 hours.
Example 4
The embodiment provides a molecular sieve catalyst for ammonia purification of an ammonia internal combustion engine, which comprises the following active components in percentage by mass: ruthenium 2% and copper 2%, the balance being molecular sieve carrier.
The preparation method comprises the following steps:
s1, mixing an ammonia type molecular sieve and a copper salt solution, and then sequentially carrying out solid-liquid separation, drying and first roasting to obtain a copper-carrying molecular sieve;
preparing a copper salt used by the copper salt solution in the step S1 to be copper nitrate; the ammonia type molecular sieve is an SSZ-13 molecular sieve; the molar concentration of copper element in the copper salt solution is 64g/L; the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and copper salt solution is 1:100; the temperature of the mixing is 60 ℃ and the time is 6 hours; the temperature of the first roasting is 600 ℃ and the time is 7 hours;
s2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and then sequentially carrying out ruthenium salt treatment, evaporation, drying and second roasting to obtain the molecular sieve catalyst;
s2, the solvent is deionized water; the temperature of the mixing is 25 ℃ and the time is 0.5h; the ruthenium salt treatment is to add ruthenium salt into the materials obtained by mixing, wherein the ruthenium salt used in the ruthenium salt treatment is trinitronitrosylruthenium, and the mass ratio of the copper-loaded molecular sieve in the ruthenium salt treatment to the ruthenium element in the used ruthenium salt is 1:0.020; the evaporation is water bath rotary evaporation, and the temperature is 60 ℃; the temperature of the second roasting is 550 ℃ and the time is 5 hours.
Example 5
The only difference from example 1 is the substitution of ruthenium salts with an equivalent amount of chloroplatinic acid.
Application example 1
The tail gas from the simulated ammonia internal combustion engine was catalytically purified using example 1, and the temperature of the catalytic purification was subjected to a gradient temperature test at 150 ℃, 175 ℃,200 ℃, 225 ℃, 250 ℃, 275 ℃, 300 ℃, 325 ℃, 350 ℃, 375 ℃ and 400 ℃;
the water content in the tail gas of the ammonia internal combustion engine is 5 percent by volume;
the total flow of the gas in the tail gas of the ammonia internal combustion engine is 500mL/min, and the airspeed is 200000h -1 。
The ammonia gas formed during operation of the ammonia internal combustion engine has a concentration of 1000ppm.
The concentration of nitric oxide formed during the operation of the ammonia internal combustion engine is 200ppm
The index of the purified gas at 300 ℃ is shown in Table 1, and the other temperature conditions are shown in FIG. 1.
Application example 2
The tail gas generated by the simulated ammonia internal combustion engine is subjected to catalytic purification by adopting the embodiment 1, wherein the temperature of the catalytic purification is 300 ℃;
the water content in the tail gas of the ammonia internal combustion engine is 5 percent by volume;
the total flow of the gas in the tail gas of the ammonia internal combustion engine is 500mL/min, and the airspeed is 200000h -1 。
The ammonia gas formed during operation of the ammonia internal combustion engine has a concentration of 1000ppm.
The concentration of nitric oxide formed during operation of the ammonia engine is 100ppm.
The index of the purified gas is shown in Table 1.
Application example 3
The tail gas generated by the simulated ammonia internal combustion engine is subjected to catalytic purification by adopting the embodiment 1, wherein the temperature of the catalytic purification is 300 ℃;
the water content in the tail gas of the ammonia internal combustion engine is 5 percent by volume;
the total flow of the gas in the tail gas of the ammonia internal combustion engine is 500mL/min, and the airspeed is 200000h -1 。
The ammonia gas formed during operation of the ammonia internal combustion engine had a concentration of 200ppm.
The concentration of nitric oxide formed during operation of the ammonia engine is 500ppm.
The index of the purified gas is shown in Table 1.
Application example 4
The tail gas generated by the simulated ammonia internal combustion engine is subjected to catalytic purification by adopting the embodiment 2, wherein the temperature of the catalytic purification is 300 ℃;
the water content in the tail gas of the ammonia internal combustion engine is 5 percent by volume;
the total flow of the gas in the tail gas of the ammonia internal combustion engine is 500mL/min, and the airspeed is 200000h -1 。
The ammonia gas formed during operation of the ammonia internal combustion engine has a concentration of 1000ppm.
The concentration of nitric oxide formed during operation of the ammonia engine is 200ppm.
The index of the purified gas is shown in Table 1.
Application example 5
Performing catalytic purification on tail gas generated by a simulated ammonia internal combustion engine by adopting the embodiment 3, wherein the temperature of the catalytic purification is 300 ℃;
the water content in the tail gas of the ammonia internal combustion engine is 5 percent by volume;
the total flow of the gas in the tail gas of the ammonia internal combustion engine is 500mL/min, and the airspeed is 200000h -1 。
The ammonia gas formed during operation of the ammonia internal combustion engine has a concentration of 1000ppm.
The concentration of nitric oxide formed during operation of the ammonia engine is 200ppm.
The index of the purified gas is shown in Table 1.
Application example 6
The tail gas generated by the simulated ammonia internal combustion engine is subjected to catalytic purification by adopting the embodiment 4, wherein the temperature of the catalytic purification is 300 ℃;
the water content in the tail gas of the ammonia internal combustion engine is 5 percent by volume;
the total flow of the gas in the tail gas of the ammonia internal combustion engine is 500mL/min, and the airspeed is 200000h -1 。
The ammonia gas formed during operation of the ammonia internal combustion engine has a concentration of 1000ppm.
The concentration of nitric oxide formed during operation of the ammonia engine is 200ppm.
The index of the purified gas is shown in Table 1.
Application example 7
The only difference from application example 2 is the use of the catalyst of example 5.
The index of the purified gas is shown in Table 1. As can be seen from comparing the data in table 1, when the active material is replaced with a combination of platinum and copper, the catalyst performance is significantly reduced in the presence of nitrogen oxides, and in the catalyst prepared by using noble metal platinum and copper as active components, the active oxygen further induces dehydrogenation of ammonia gas into nitrogen atoms to generate nitrogen gas due to dissociation of oxygen gas into active oxygen at the surface of noble metal platinum. At the same time, the combination of active oxygen and nitrogen atoms generates nitric oxide, and nitric oxide and ammonia gas can generate nitrous oxide byproducts on noble metal platinum, so that the selectivity of nitrogen is lower. When the catalyst taking ruthenium and copper as active components exists in nitric oxide, nitric oxide and ammonia gas can not or little generate nitrous oxide byproducts on the active component ruthenium, so that ammonia gas can be removed better, and the problem of purifying tail gas of an ammonia internal combustion engine in actual conditions is solved.
TABLE 1
Figure BDA0004086609900000141
Figure BDA0004086609900000151
As is clear from the results of the above application examples, the low-temperature activity and nitrogen selectivity of the catalyst ammoxidation reaction are improved by the synergistic effect of metals by introducing ruthenium and copper as active components. The noble metal ruthenium has higher activity and can ensure the smooth progress of the ammoxidation reaction. The active component copper has the capability of reducing nitrogen oxides, can effectively reduce the nitrogen oxides in the tail gas, and solves the problem of tail gas purification when a small amount of nitrogen oxides exist in the tail gas of the current ammonia internal combustion engine.
It is stated that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e., it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (10)

1. A method for preparing a catalyst for purifying tail gas of an ammonia internal combustion engine, the method comprising:
s1, mixing an ammonia type molecular sieve and a copper salt solution, performing solid-liquid separation and first roasting to obtain a copper-loaded molecular sieve;
s2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and sequentially carrying out ruthenium salt treatment, evaporation and second roasting to obtain the catalyst for purifying the tail gas of the ammonia internal combustion engine.
2. The method of manufacture of claim 1, wherein the ammonia-type molecular sieve comprises 1 or a combination of at least 2 of a ZSM-5 molecular sieve, an SSZ-13 molecular sieve, or a Y molecular sieve;
preferably, the copper salt used for the copper salt solution of step (1) comprises 1 or a combination of at least 2 of copper chloride, copper sulfate, copper nitrate or copper acetate, preferably copper nitrate;
preferably, the concentration of copper element in the copper salt solution is 3.2-128g/L;
preferably, the ammonia type molecular sieve and copper salt solution have a solid-to-liquid ratio g/mL of 1 (10-150).
3. The method of claim 1 or 2, wherein the ammonia-type molecular sieve and copper salt solution are mixed for a period of time ranging from 5 to 8 hours.
4. A method according to any one of claims 1 to 3, wherein the first calcination temperature is 500 to 700 ℃;
preferably, the time of the first calcination is 5 to 9 hours.
5. The method of any one of claims 1-4, wherein the solvent comprises water and/or ethanol;
preferably, the copper-loaded molecular sieve and the solvent are mixed for a period of 1 to 4 hours.
6. The method according to any one of claims 1 to 5, wherein the ruthenium salt treatment is to add ruthenium salt to a material obtained by mixing a copper-carrying molecular sieve and a solvent;
preferably, the ruthenium salt used in the ruthenium salt treatment comprises 1 or a combination of at least 2 of ruthenium trichloride, ruthenium trinitronitrosyl or ruthenium acetate, preferably ruthenium trinitrosyl;
preferably, the mass ratio of the copper-carrying molecular sieve in the ruthenium salt treatment to the ruthenium element in the ruthenium salt is 1 (0.005-0.05).
7. The method of any one of claims 1-6, wherein the evaporating comprises water bath rotary evaporation;
preferably, the temperature of the evaporation is 50-80 ℃;
preferably, the temperature of the second firing is 400-700 ℃;
preferably, the second calcination is carried out for a period of 4 to 8 hours.
8. The method of any one of claims 1-7, wherein the method of preparation comprises:
s1, mixing an ammonia type molecular sieve and a copper salt solution, performing solid-liquid separation and first roasting to obtain a copper-loaded molecular sieve;
s2, mixing the copper-carrying molecular sieve obtained in the step S1 with a solvent, and sequentially carrying out ruthenium salt treatment, evaporation and second roasting to obtain a catalyst for purifying the tail gas of the ammonia internal combustion engine;
the ammonia type molecular sieve in S1 comprises 1 or at least 2 of ZSM-5 molecular sieve, SSZ-13 molecular sieve or Y molecular sieve; the copper salt used in the copper salt solution comprises 1 or a combination of at least 2 of copper chloride, copper sulfate, copper nitrate or copper acetate; the concentration of copper element in the copper salt solution is 3.2-128g/L; the solid-to-liquid ratio g/mL of the ammonia type molecular sieve and copper salt solution is 1 (10-150); the mixing time of the ammonia type molecular sieve and the copper salt solution is 5-8h; the temperature of the first roasting is 500-700 ℃; the first roasting time is 5-9h;
the solvent in S2 comprises water and/or ethanol; the mixing time of the copper-carrying molecular sieve and the solvent is 1-4 hours; the ruthenium salt treatment is to add ruthenium salt into a material obtained after the copper-carrying molecular sieve and the solvent are mixed; the ruthenium salt used in the ruthenium salt treatment comprises 1 or a combination of at least 2 of ruthenium trichloride, ruthenium trinitronitrosyl or ruthenium acetate; the mass ratio of the copper-carrying molecular sieve in the ruthenium salt treatment to the ruthenium element in the ruthenium salt is 1 (0.005-0.05); the evaporation comprises water bath rotary evaporation; the evaporating temperature is 50-80 ℃; the temperature of the second roasting is 400-700 ℃; the second roasting time is 4-8h.
9. A catalyst for purifying an exhaust gas of an ammonia internal combustion engine obtained by the production method as set forth in any one of claims 1 to 8, characterized in that the catalyst for purifying an exhaust gas of an ammonia internal combustion engine comprises an active component in mass percent: 0.5-5% of ruthenium, 2-5% of copper and the balance of molecular sieve carrier.
10. Use of the catalyst for purifying exhaust gas of an ammonia internal combustion engine obtained by the production method according to any one of claims 1 to 8, characterized in that the use comprises catalytic purification of exhaust gas formed in operation of the ammonia internal combustion engine with the catalyst for purifying exhaust gas of an ammonia internal combustion engine;
the temperature of the catalytic purification is 200-500 ℃;
the water content in the tail gas of the ammonia internal combustion engine is 5-15% by volume;
the concentration of ammonia in the tail gas formed by the ammonia internal combustion engine is 500-2000ppm;
the concentration of nitric oxide in the tail gas formed by the ammonia internal combustion engine is 100-500ppm.
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