CN107469808A - For the preparation and application of the SCR catalyst for removing ship tail gas nitrogen oxides - Google Patents

For the preparation and application of the SCR catalyst for removing ship tail gas nitrogen oxides Download PDF

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CN107469808A
CN107469808A CN201710755756.0A CN201710755756A CN107469808A CN 107469808 A CN107469808 A CN 107469808A CN 201710755756 A CN201710755756 A CN 201710755756A CN 107469808 A CN107469808 A CN 107469808A
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scr catalyst
nitrogen oxides
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ship tail
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CN107469808B (en
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刘庆岭
郭铭玉
李轩
付振超
马德刚
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Tianjin University
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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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—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
    • B01D53/74—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
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20784—Chromium

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Abstract

The invention discloses a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, its step is：Cr and Zr inorganic salts are made into the solution A and B that molar concentration is 0.5 1mol/L, wherein Cr after mixing respectively3+And Zr4+Mol ratio be (5:1)‑(1:3)；Ammoniacal liquor is made into the solution that molar concentration is 0.3 1mol/L；Ammonia spirit is instilled dropwise in the container for filling mixed solution A and B, be stirred vigorously simultaneously, by adjusting the drop rate of ammonia spirit, it is 8 10 to make its titration end-point pH value, continues to stir 30 60min, then stands 3 6h, filters；It is neutrality by Washing of Filter Cake to cleaning solution, the presoma of SCR catalyst is obtained after drying；Presoma is placed in Muffle furnace, under 550 650 DEG C of air atmosphere, 3 6h is calcined, that is, obtains the SCR catalyst for removing ship tail gas nitrogen oxides.Catalyst prepared by the present invention has the advantages that catalytic activity high and low temperature sulfur resistance is strong, cheap, has good application value and prospect.

Description

For the preparation and application of the SCR catalyst for removing ship tail gas nitrogen oxides
Technical field
The invention belongs to catalyst preparation applied technical field, more particularly to one kind to be applied to remove ship tail gas nitrogen oxidation Thing (NOx) the excellent SCR catalyst of low temperature resistance to SO_2 preparation method.
Background technology
Shipping industry in China's obtains large development, especially marine diesel tail gas pollution problem, nitrogen oxidation in recent years The discharge of thing, cause internal and international extensive concern, and the nitrogen oxides that China's major part fuel oil steamer is discharged far reaches Less than international requirement, as a harbour big country for occupying the Port of the seven seat world ten, administering Pollution From Ships problem has turned into The most important thing of China's Future Development.Nitrogen oxides (NOx) include multiple compounds, such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), nitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4) and dinitrogen pentoxide (N2O5) etc., ship tail The nitrogen oxides of gas discharge mainly includes NO and NO2.Under solar irradiation, NOxExist jointly with organic matters such as alkene, by one Serial complicated chemical reaction can produce photochemical fog, and it has strong oxidizing property, can make crop production reduction, stimulates the breathing of people Road and eyes are lethal when serious.NOxAcid rain can be formed with rainwater effect, corrodes vegetation and building, the sedimentation of nitrate granules thing To soil or water body, cause acidifying, by contaminated soil and underground water.Nitrogen oxides enters upper atmosphere can be broken to ozone layer generation Bad effect, and then the environmental pollution such as Global climate change effect and ecological-environment differention can be caused.
At present, selective catalytic reduction SCR (Selective Catalytic Reduction) is that world's utilization is most wide The general and best effect method for removing denitrification.The core of SCR technology is catalyst, thus catalyst needs to have height and urged The features such as changing active, excellent resistance to SO_2 and stability.Marine diesel is divided into two-stroke and four-stroke engine, four stroke bavins Oil machine delivery temperature is of a relatively high, and two stroke diesel engine delivery temperature is relatively low (being less than 250 DEG C), it is therefore desirable to different activities temperature Spending the SCR catalyst of window makes NOxRemoval reaches optimal effect.The SCR catalyst being widely used at present has traditional vanadium tungsten Titanium catalyst and Cu-SSZ-13 catalyst, but traditional vanadium tungsten titanium catalyst active window temperature is high, limits it in low temperature ring Application in border.Although Cu-SSZ-13 catalyst has an excellent catalytic performance, but its low temperature water resistant resistance to SO_2 is poor and valency Lattice are expensive, limit its application in the ship tail gas containing high-sulfur.
The content of the invention
The problem of existing for above-mentioned ship discharge nitrogen oxides treatment, the present invention provides a kind of for removing ship tail gas The preparation method of the SCR catalyst of nitrogen oxides, is a kind of new metal oxide catalyst, and the catalyst cryogenic property is excellent It is different, and sulfur resistance is good, cost is cheap, and the control that nitrogen oxides is discharged especially for ship has very important significance.
In order to solve the above-mentioned technical problem, a kind of SCR for being used to remove ship tail gas nitrogen oxides proposed by the present invention is urged The preparation method of agent, comprises the following steps：
Step 1: Cr and Zr inorganic salts are dissolved in the water by a certain percentage respectively, it is 0.5-1mol/ to be made into molar concentration L solution A and solution B, solution A and solution B are then mixed into solution C, in solution C, Cr3+And Zr4+Mol ratio be (5: 1)-(1:3)；Ammonia spirit is made into the solution D that molar concentration is 0.3-1mol/L；
Step 2: solution D is instilled in the container for filling solution C dropwise, it is stirred vigorously simultaneously, by adjusting solution D Drop rate controls the pH value of mixed liquor, and to make its titration end-point pH value be 8-10, continues to stir 30-60min, then stands 3- 6h, it is filtrated to get filter cake；
It is neutrality to cleaning solution, before obtaining SCR catalyst after drying Step 3: by filter cake with water washing is distilled 3-5 times Drive body；
Step 4: the presoma of above-mentioned catalyst is placed in Muffle furnace, under 550-650 DEG C of air atmosphere, roasting 3-6h, that is, obtain the SCR catalyst for removing ship tail gas nitrogen oxides.
Further, in the present invention, Cr, Zr inorganic salts are in corresponding nitrate, chlorate and sulfate It is a kind of.The condition of drying process in step 3 is that 10-12h is dried at 100-120 DEG C.
It is 130- that being used for prepared by the present invention is removed into the SCR catalyst of ship tail gas nitrogen oxides in reaction temperature 330 DEG C, using ammonia as reducing agent, 500ppm NO, 500ppm NH3, 10%O2, N2Make Balance Air, control total gas flow rate exists Bed reaction is fixed under conditions of 300ml/min.Resistance to SO_2 test temperature is 230 DEG C, and concentration is 100ppm SO2.Treat each The concentration of NO in reacting furnace inlet and outlet gas is determined after temperature spot is stable, and presses (reacting furnace import NO concentration-reacting furnace Export NO concentration)/(reacting furnace import NO concentration) × 100% calculating conversion ratio.The SCR catalyst that the present invention is prepared exists Under the conditions of 180~280 DEG C, its NO conversion ratio is up to 72~98%.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) the inventive method prepares Reduction of NO using common and economical inorganic salts and alkalixCatalyst；
(2) catalyst is to NOxPurification there is preferable selectivity and clearance, and operating temperature range can be 130-330℃；
(3) catalyst is to SO2There is preferable resistant function, in low temperature and SO2Under the conditions of existing, for NOxIt is net Change works well.
Brief description of the drawings
Fig. 1 is comparative example 1 and 1-4 catalyst SCR activity test result figures of the embodiment of the present invention；
Fig. 2 is comparative example 2 and 5-7 catalyst SCR activity test result figures of the embodiment of the present invention；
Fig. 3 is comparative example 1 and 1-4 catalyst resistance to SO_2 test result figures of the embodiment of the present invention；
Fig. 4 is comparative example 2 and 5-7 catalyst resistance to SO_2 test result figures of the embodiment of the present invention.
Embodiment
Technical solution of the present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, described is specific Only the present invention is explained for embodiment, is not intended to limit the invention.
Embodiment 1, a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, including following step Suddenly：
(1) chromium sulfate and zirconium chloride are dissolved in the water by a certain percentage respectively, it is 0.5mol/ to be made into molar concentration respectively L and 1mol/L solution A and solution B, solution A and solution B are then mixed into solution C, in solution C, Cr3+And Zr4+Mole Than for 5:1；Ammonia spirit is made into the solution D that molar concentration is 0.3mol/L.
(2) solution D is instilled dropwise in the beaker for filling mixed solution A and B, be stirred vigorously simultaneously, by adjusting solution C Drop rate control pH of mixed, its titration end-point pH is in 9, continue to stir 60min, then stand 4h, filter To filter cake.
(3) filter cake is neutrality to cleaning solution, SCR catalyst is obtained after 100 DEG C of dry 11h with water washing is distilled 5 times Presoma；
(4) presoma of above-mentioned catalyst is placed in Muffle furnace, under 550 DEG C and air atmosphere, is calcined 4h, that is, obtains For removing the SCR catalyst of ship tail gas nitrogen oxides.
The test result of the SCR catalyst SCR activity that embodiment 1 is prepared as shown in figure 1, at 180~280 DEG C, Its NO conversion ratio is 72%~85%, and the sulfur resistance at 230 DEG C is as shown in Figure 3.
Embodiment 2, a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, including following step Suddenly：
(1) chromic nitrate and zirconium nitrate are dissolved in the water by a certain percentage respectively, it is 0.5mol/ to be made into molar concentration respectively L solution A and B, solution A and solution B are then mixed into solution C, in solution C, Cr3+And Zr4+Mol ratio be 4:1；By ammonia The aqueous solution is made into the solution D that molar concentration is 0.5mol/L.
(2) solution D is instilled in the beaker for filling mixed solution C dropwise, be stirred vigorously simultaneously, by adjusting solution C Drop rate controls pH of mixed, its titration end-point pH is in 10, continues to stir 40min, then stands 3h, filters.
(3) filter cake is neutrality to cleaning solution, SCR catalyst is obtained after 120 DEG C of dry 12h with water washing is distilled 4 times Presoma；
(4) presoma of above-mentioned catalyst is placed in Muffle furnace, under 550 DEG C and air atmosphere, is calcined 5h, that is, obtains For removing the SCR catalyst of ship tail gas nitrogen oxides.
The test result of the SCR catalyst SCR activity that embodiment 2 is prepared as shown in figure 1, at 180~280 DEG C, Its NO conversion ratio is 86%~90% or so, and the sulfur resistance at 230 DEG C is as shown in Figure 3.
Embodiment 3, a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, including following step Suddenly：
(1) chromium chloride and zirconium sulfate are dissolved in the water by a certain percentage respectively, it is 0.8mol/ to be made into molar concentration respectively L and 0.6mol/L solution A and B, is then mixed into solution C by A and B solution, makes wherein Cr3+And Zr4+Mol ratio be 3:1； Ammonia spirit is made into the solution D that molar concentration is 1mol/L.
(2) solution D is instilled in the beaker for filling mixed solution C dropwise, be stirred vigorously simultaneously, by adjusting solution C Drop rate controls pH of mixed, its titration end-point pH is in 9, continues to stir 50min, then stands 6h, filters.
(3) filter cake is neutrality to cleaning solution with water washing is distilled 3 times, obtains being used to be catalyzed NO after 110 DEG C of dry 11hx The precursor of catalyst；
(4) above-mentioned catalyst precarsor is placed in Muffle furnace, under 600 DEG C and air atmosphere, is calcined 4h, that is, obtains low temperature Resistance to SO_2 it is excellent remove denitrification (NOx) catalyst.
The test result of the SCR catalyst SCR activity that embodiment 3 is prepared as shown in figure 1, at 180~280 DEG C, Its NO conversion ratio is 88%~94%, and the sulfur resistance at 230 DEG C is as shown in Figure 3.
Embodiment 4, a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, including following step Suddenly：
(1) chromium sulfate and zirconium nitrate are dissolved in the water by a certain percentage respectively, it is 0.7mol/ to be made into molar concentration respectively L and 0.9mol/L solution A and B, is then mixed into solution C by A and B solution, makes wherein Cr3+And Zr4+Mol ratio be 2:1； Ammonia spirit is made into the solution D that molar concentration is 0.7mol/L.
(2) solution D is instilled in the beaker for filling mixed solution C dropwise, be stirred vigorously simultaneously, by adjusting solution C Drop rate controls pH of mixed, its titration end-point pH is in 9, continues to stir 40min, then stands 5h, filters.
(3) filter cake is neutrality to cleaning solution with water washing is distilled 5 times, obtains being used to be catalyzed NO after 100 DEG C of dry 12hx The precursor of catalyst；
(4) above-mentioned catalyst precarsor is placed in Muffle furnace, under 650 DEG C and air atmosphere, is calcined 3h, that is, obtains low temperature Resistance to SO_2 it is excellent remove denitrification (NOx) catalyst.
The test result of the SCR catalyst SCR activity that embodiment 4 is prepared as shown in figure 1, at 180~280 DEG C, Its NO conversion ratio is 85%~92%, and the sulfur resistance at 230 DEG C is as shown in Figure 3.
Embodiment 5, a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, including following step Suddenly：
(1) chromic nitrate and zirconium nitrate are dissolved in the water by a certain percentage respectively, it is 0.8mol/L to be made into molar concentration Solution A and B, A and B solution are then mixed into solution C, make wherein Cr3+And Zr4+Mol ratio be 1:1；By ammonia spirit It is made into the solution D that molar concentration is 0.8mol/L.
(2) solution D is instilled in the beaker for filling mixed solution C dropwise, be stirred vigorously simultaneously, by adjusting solution C Drop rate controls pH of mixed, its titration end-point pH is in 10, continues to stir 50min, then stands 4h, filters.
(3) filter cake is neutrality to cleaning solution with water washing is distilled 4 times, obtains being used to be catalyzed NO after 120 DEG C of dry 10hx The precursor of catalyst；
(4) above-mentioned catalyst precarsor is placed in Muffle furnace, under 550 DEG C and air atmosphere, is calcined 6h, that is, obtains low temperature Resistance to SO_2 it is excellent remove denitrification (NOx) catalyst.
The test result of the SCR catalyst SCR activity that embodiment 5 is prepared as shown in Fig. 2 at 180~280 DEG C, Its NO conversion ratio is 95%~98%, and the sulfur resistance at 230 DEG C is as shown in Figure 4.
Embodiment 6, a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, including following step Suddenly：
(1) chromium sulfate and zirconium sulfate inorganic salts are dissolved in the water by a certain percentage respectively, being made into molar concentration respectively is 1mol/L and 0.5mol/L solution A and B, is then mixed into solution C by A and B solution, makes wherein Cr3+And Zr4+Mol ratio For 1:2；Ammonia spirit is made into the solution D that molar concentration is 0.6mol/L.
(2) solution D is instilled in the beaker for filling mixed solution C dropwise, be stirred vigorously simultaneously, by adjusting solution C Drop rate controls pH of mixed, its titration end-point pH is in 8, continues to stir 30min, then stands 5h, filters.
(3) filter cake is neutrality to cleaning solution with water washing is distilled 3 times, obtains being used to be catalyzed NO after 110 DEG C of dry 12hx The precursor of catalyst；
(4) above-mentioned catalyst precarsor is placed in Muffle furnace, under 600 DEG C and air atmosphere, is calcined 4h, that is, obtains low temperature Resistance to SO_2 it is excellent remove denitrification (NOx) catalyst.
The test result of the SCR catalyst SCR activity that embodiment 6 is prepared as shown in Fig. 2 at 180~280 DEG C, Its NO conversion ratio is 88%~95%, and the sulfur resistance at 230 DEG C is as shown in Figure 4.
Embodiment 7, a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, including following step Suddenly：
(1) chromium chloride and zirconium chloride inorganic salts are dissolved in the water by a certain percentage respectively, being made into molar concentration respectively is 0.6mol/L and 0.8mol/L solution A and B, is then mixed into solution C by A and B solution, makes wherein Cr3+And Zr4+Mole Than for 1:3；Ammonia spirit is made into the solution D that molar concentration is 0.4mol/L.
(2) solution D is instilled in the beaker for filling solution C dropwise, be stirred vigorously simultaneously, by the dropwise addition for adjusting solution C Speed controls pH of mixed, its titration end-point pH is in 8, continues to stir 60min, then stands 6h, filters.
(3) filter cake is neutrality to cleaning solution with water washing is distilled 4 times, obtains being used to be catalyzed NO after 110 DEG C of dry 11hx The precursor of catalyst；
(4) above-mentioned catalyst precarsor is placed in Muffle furnace, under 650 DEG C and air atmosphere, is calcined 3h, that is, obtains low temperature Resistance to SO_2 it is excellent remove denitrification (NOx) catalyst.
The test result of the SCR catalyst SCR activity that embodiment 7 is prepared as shown in Fig. 2 at 180~280 DEG C, Its NO conversion ratio is 92%~98%, and the sulfur resistance at 230 DEG C is as shown in Figure 4.
Comparative example 1, a kind of preparation method for being used to go the SCR catalyst of denitrification, comprise the following steps：
(1) chromic nitrate and zirconium sulfate are dissolved in the water by a certain percentage respectively, it is 1.0mol/L's to be made into molar concentration Solution A and solution B, solution A and solution B are then mixed into solution C, in solution C, Cr3+And Zr4+Mol ratio be 5:0；Will Ammonia spirit is made into the solution D that molar concentration is 1mol/L；
(2) solution D is instilled in the beaker for filling solution C dropwise, be stirred vigorously simultaneously, by the dropwise addition for adjusting solution D Speed controls the pH value of mixed liquor, and it is 8 to make its titration end-point pH value, continues to stir 30min, then stands 3h, be filtrated to get Filter cake；
(3) be neutrality to cleaning solution by filter cake distillation water washing 3 times, after 120 DEG C of dry 10h after obtain SCR catalyst Presoma；
(4) presoma of above-mentioned catalyst is placed in Muffle furnace, under 500 DEG C of air atmosphere, is calcined 6h, that is, obtains For going the SCR catalyst of denitrification.
The test result of the SCR catalyst SCR activity that comparative example 1 is prepared as shown in figure 1, at 180~280 DEG C, Its NO conversion ratio is 42%~53%, and the sulfur resistance at 230 DEG C is as shown in Figure 3.
Comparative example 2, a kind of preparation method for being used to go the SCR catalyst of denitrification, comprise the following steps：
(1) chromium chloride and zirconium sulfate inorganic salts are dissolved in the water by a certain percentage respectively, being made into molar concentration is 0.6mol/L solution A and B, is then mixed into solution C by A and B solution, makes wherein Cr3+And Zr4+Mol ratio be 0:3；Will Ammonia spirit is made into the solution D that molar concentration is 0.6mol/L.
(2) solution D is instilled in the beaker for filling mixed solution C dropwise, be stirred vigorously simultaneously, by adjusting solution C Drop rate controls pH of mixed, its titration end-point pH is in 10, continues to stir 60min, then stands 5h, filters.
(3) filter cake is neutrality to cleaning solution with water washing is distilled 3 times, obtains being used to be catalyzed NO after 120 DEG C of dry 10hx The precursor of catalyst；
(4) above-mentioned catalyst precarsor is placed in Muffle furnace, under 550 DEG C and air atmosphere, is calcined 4h, that is, is used for Go the SCR catalyst of denitrification.
The test result of the SCR catalyst SCR activity that comparative example 2 is prepared as shown in Fig. 2 at 180~280 DEG C, Its NO conversion ratio is 20%~28%, and the sulfur resistance at 230 DEG C is as shown in Figure 4.
To sum up, comparative example 1 and 2 and the embodiment of the present invention 1~7 prepare gained catalyst as shown in Figure 1, Figure 2, Figure 3 and Figure 4 NO conversion ratio and sulfur resistance curve, it can be deduced that, using preparation method of the present invention be prepared be used for remove ship Tail gas nitrogen oxide (NOx) SCR catalyst, catalyst catalytic performance major control factors are Cr3+And Zr4+Mol ratio, and Inorganic Salts, titration end-point pH, time of repose is stirred, distilled water washing times, are dried and the sintering temperature time is to its activity Influence is smaller, especially has in 180~280 DEG C in 130-330 DEG C of scope and efficiently removes NOxPerformance, Cr3+And Zr4+'s Mol ratio is 1:It removes NO when 1xPerformance it is best, and there is excellent resistance to SO_2, Cr at low ambient temperatures3+And Zr4+'s Mol ratio is 4:Its sulfur resistance is best when 1, i.e., SO has been may be implemented in certain temperature2In the presence of for NOx's Efficiently remove, can be widely applied to NO in sulfur-bearing ship tail gasxPurification.
Although above in conjunction with accompanying drawing, invention has been described, and the invention is not limited in above-mentioned specific implementation Mode, above-mentioned embodiment is only schematical, rather than restricted, and one of ordinary skill in the art is at this Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to the present invention's Within protection.

Claims (4)

1. a kind of preparation method for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, it is characterised in that including following step Suddenly：
Step 1: Cr and Zr inorganic salts are dissolved in the water by a certain percentage respectively, it is 0.5-1mol/L's to be made into molar concentration Solution A and solution B, solution A and solution B are then mixed into solution C, in solution C, Cr3+And Zr4+Mol ratio be (5:1)- (1:3)；Ammonia spirit is made into the solution D that molar concentration is 0.3-1mol/L；
Step 2: solution D is instilled in the container for filling solution C dropwise, it is stirred vigorously simultaneously, by the dropwise addition for adjusting solution D Speed controls the pH value of mixed liquor, and to make its titration end-point pH value be 8-10, continues to stir 30-60min, then stands 3-6h, It is filtrated to get filter cake；
Step 3: filter cake is neutrality to cleaning solution, the forerunner of SCR catalyst is obtained after drying with water washing is distilled 3-5 times Body；
Step 4: the presoma of above-mentioned catalyst is placed in Muffle furnace, under 550-650 DEG C of air atmosphere, 3-6h is calcined, Obtain the SCR catalyst for removing ship tail gas nitrogen oxides.
2. being used for the preparation method for removing the SCR catalyst of ship tail gas nitrogen oxides according to claim 1, its feature exists In：Cr, Zr inorganic salts are one kind in corresponding nitrate, chlorate and sulfate.
3. being used for the preparation method for removing the SCR catalyst of ship tail gas nitrogen oxides according to claim 1, its feature exists In：The condition of drying process in step 3 is that 10-12h is dried at 100-120 DEG C.
4. a kind of application for being used to remove the SCR catalyst of ship tail gas nitrogen oxides, it is characterised in that nitrogen oxides is sulfur-bearing NO and NO in ship tail gas2；It will be used to remove ship tail gas made from the preparation method as described in any in claims 1 to 3 Bed reaction is fixed under conditions of being 130~330 DEG C in reaction temperature in the SCR catalyst of nitrogen oxides, using ammonia as reduction Agent, control total gas flow rate is in 300ml/min.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108554400A (en) * 2018-06-12 2018-09-21 天津大学 Preparation and application for the low temperature sulfur resistive SCR catalyst for removing ship tail gas nitrogen oxides
CN108772058A (en) * 2018-07-05 2018-11-09 天津大学 Preparation method for the Mn-Zr-Cr catalyst for removing gas fired-boiler tail gas nitrogen oxide
CN109060014A (en) * 2018-07-16 2018-12-21 交通运输部水运科学研究所 A kind of marine exhaust discharge compliance determines and violation ship identification method and system
CN109158109A (en) * 2018-09-15 2019-01-08 天津大学 A kind of application of the preparation method and middle low temperature sulfur resistive SCR catalyst of environmental-friendly middle low temperature sulfur resistive SCR catalyst
CN109174101A (en) * 2018-09-15 2019-01-11 天津大学 The preparation method of low temperature sulfur resistive SCR catalyst and the application of the catalyst

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