CN115869992A - Coking flue gas desulfurization and denitrification catalyst and preparation method thereof - Google Patents
Coking flue gas desulfurization and denitrification catalyst and preparation method thereof Download PDFInfo
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- CN115869992A CN115869992A CN202211647900.6A CN202211647900A CN115869992A CN 115869992 A CN115869992 A CN 115869992A CN 202211647900 A CN202211647900 A CN 202211647900A CN 115869992 A CN115869992 A CN 115869992A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 69
- 230000023556 desulfurization Effects 0.000 title claims abstract description 69
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003546 flue gas Substances 0.000 title claims abstract description 36
- 238000004939 coking Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 24
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 polyoxyethylene Polymers 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002241 glass-ceramic Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000007873 sieving Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The application discloses a coking flue gas desulfurization and denitrification catalyst and a preparation method thereof, and relates to the technical field of desulfurization and denitrification. The catalyst comprises, by weight, 30-60 parts of active metal, 15-35 parts of catalytic assistant, 70-100 parts of carrier and 90-120 parts of forming assistant, wherein the active metal is at least one of VIB, VIIB and VIII group metals; the auxiliary agent is non-metal auxiliary agent P, B, F or one or more of metal auxiliary agents Mg, ca, la and Ce; the carrier is an H-beta molecular sieve, the H-beta molecular sieve is pretreated and loaded with active metal to realize the desulfurization and denitrification of the flue gas, and the flue gas is made into a honeycomb type, so that the flue gas has high desulfurization and denitrification efficiency and certain mechanical strength.
Description
Technical Field
The application relates to a coking flue gas desulfurization and denitrification catalyst and a preparation method thereof, belonging to the field of desulfurization and denitrification.
Background
The application of the coal-fired boiler is one of the main reasons for causing the atmospheric environment pollution, the coal-fired boiler has large quantity and wide range, the coal consumption is increased year by year, a large amount of harmful gases such as sulfur oxides, nitrogen oxides and other harmful substances are discharged every year, and the coal-fired boiler mostly requires to control the discharge of sulfur dioxide and nitrogen oxide along with the national improvement of the pollutant content standard in the waste gas. The removal of sulfur dioxide and nitrogen oxides in coal-fired flue gas and motor vehicles is the main task of atmospheric pollution control in China at present.
In the conventional common flue gas desulfurization and denitrification method, the steps are complicated, a good desulfurization and denitrification effect needs to be obtained through reasonable matching of different catalysts, and a single catalyst is difficult to have high desulfurization and denitrification rate.
Disclosure of Invention
In order to solve the problems, the invention provides a coking flue gas desulfurization and denitrification catalyst which is high in desulfurization and denitrification rate.
The invention is realized by the following technical scheme: a coking flue gas desulfurization and denitrification catalyst comprises, by weight, 30-60 parts of active metal, 15-35 parts of catalytic promoter, 70-100 parts of carrier and 90-120 parts of forming promoter;
the active metal is at least one of VIB, VIIB and VIII group metals;
the auxiliary agent is non-metal auxiliary agent P, B, F or one or more of metal auxiliary agents Mg, ca, la and Ce;
the carrier is an H-beta molecular sieve, and the H-beta molecular sieve is pretreated;
the pretreatment mainly comprises the following steps:
(1) Placing the H-beta molecular sieve in a muffle furnace, heating to 400-600 ℃, roasting for 3-5H, and cooling to room temperature for later use;
(2) Putting the carrier treated in the step (1) into a beaker, adding deionized water, an active metal salt solution and an auxiliary agent, and uniformly stirring;
(3) Placing the sample treated in the step (2) in a constant-temperature water bath kettle at 35-55 ℃ for soaking for 7-9h, transferring the sample into a drying box at 100-120 ℃, and drying for 11-14h;
(4) And (4) placing the dried sample in the step (3) into a muffle furnace, roasting for 3-5h at 500-600 ℃, and cooling to room temperature to obtain the required sample.
Preferably, the forming aid comprises, by weight, 3-6 parts of an organic binder, 2-6 parts of a plasticizer, 30-50 parts of a structural aid, 40-60 parts of red mud and 80-110 parts of an inorganic binder;
the organic adhesive is at least one of carboxymethyl cellulose, sesbania powder and polyvinyl alcohol;
the plasticizer is polyoxyethylene or polyvinyl chloride;
the structural auxiliary agent is glass fiber or ceramic fiber;
the inorganic binder is at least one of boehmite, silica sol and alumina sol.
Preferably, the carrier treated in the step (1) is placed in a beaker, deionized water is added while stirring until no excess deionized water is separated out, and the amount of the deionized water used is the same as that in the step (2).
Preferably, the active metal is at least one of Co, ni, mn, cr and Fe.
Preferably, the mass ratio of the active metal salt solution to the molecular sieve is (0.2-0.5): 1.
preferably, the specific surface area of the H-beta molecular sieve is 400-500m 2 (ii)/g, pore diameter is 0.3-0.5nm.
Preferably, the sample obtained in the step (4) is placed on a tablet press, 4-7min is pressed under the pressure of 15-25MPa, and the sample is sieved to 20-40 meshes for later use.
According to another aspect of the application, a preparation method of the coking flue gas desulfurization and denitrification catalyst is provided, which comprises the following steps:
accurately weighing 3-6 parts of the organic binder, 2-6 parts of the plasticizer, 40-60 parts of red mud, 80-110 parts of the inorganic binder, 70-100 parts of the pretreated carrier and 100 parts of deionized water by weight, and placing the mixture into a stirrer to be uniformly mixed;
weighing 30-50 parts of structural auxiliary agent, putting into a stirrer, and fully mixing to form uniform and plastic pug;
thirdly, putting the pug obtained in the second step under a vacuum condition for aging for 15-25h;
and (IV) putting the aged pug into a horizontal bar reciprocating hydraulic extruder, extruding and molding to obtain an integral honeycomb desulfurization and denitrification catalyst, and calcining to obtain the coking flue gas desulfurization and denitrification catalyst.
Preferably, in the step (IV), the calcination treatment process is as follows: the integral honeycomb desulfurization and denitrification catalyst is dried for 45-55h at room temperature, then is dried for 4-8h in a drying box at 70-90 ℃, and is placed in a calcining kiln for two-section calcining after the quality is constant.
Preferably, the two-stage calcination is carried out at 250-350 ℃ and 450-600 ℃ respectively, and the calcination time is 4-6h.
Benefits of the present application include, but are not limited to:
1. according to the coking flue gas desulfurization and denitrification catalyst provided by the application, the carrier is selected from the H-beta molecular sieve, the unique and ordered porous structure of the H-beta molecular sieve is favorable for the diffusion of reactants and products, the large specific surface area provides enough space for chemical adsorption and reaction, and the reaction rate can be accelerated while the selectivity is improved.
2. According to the coking flue gas desulfurization and denitrification catalyst provided by the application, the active metal is loaded on the H-beta molecular sieve by adopting an impregnation method, so that the low-temperature catalytic oxidation activity of the catalyst is improved.
3. According to the coking flue gas desulfurization and denitrification catalyst provided by the application, the auxiliary agent is added, so that the acid-base sites on the surface of the carrier can be effectively adjusted, the agglomeration of active species on the surface of the catalyst is inhibited, the alkaline earth metal auxiliary agent and the carrier form a mixed oxide structure, the interaction of active components and the carrier is weakened, and the dispersion of an active phase on the surface of the catalyst is increased.
4. According to the coking flue gas desulfurization and denitrification catalyst provided by the application, the catalyst is made into a honeycomb shape, active ingredients are uniformly distributed in the catalyst, and even if the surface of the catalyst is abraded, the catalyst can still keep stronger activity, and the honeycomb catalyst can be applied to high ash and low ash conditions and has the advantages of large opening area, small pressure drop, difficulty in blockage, wide reaction temperature range, high activity, strong selectivity and the like.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the present invention, and the skilled person can easily substitute or modify the present invention. Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
Example 1
The pretreatment of the H-beta molecular sieve carrier comprises the following steps:
(1) Placing 70 parts of H-beta molecular sieve in a muffle furnace, heating to 400 ℃, roasting for 3 hours, and cooling to room temperature for later use;
(2) And (2) putting the H-beta molecular sieve treated in the step (1) into a beaker, adding deionized water, 30 parts of manganese nitrate solution and 15 parts of non-metal additive P, and uniformly stirring.
(3) And (3) placing the sample treated in the step (2) in a constant-temperature water bath kettle at 35 ℃ for soaking for 7h, transferring the sample into a drying box at 100 ℃ and drying for 11h.
(4) Placing the dried sample in the step (3) in a muffle furnace, roasting for 3h at 500 ℃, and cooling to room temperature to obtain a required sample;
(5) And (3) placing the sample obtained in the step (4) on a tablet machine, tabletting 4 min under the pressure of 15MPa, and sieving the sample to 20 meshes for later use.
The preparation method of the coking flue gas desulfurization and denitrification catalyst comprises the following steps:
accurately weighing 3 parts of polyvinyl alcohol, 2-6 parts of polyethylene oxide, 40-60 parts of red mud, 80-110 parts of glass fiber, 70 parts of pretreated carrier and 100 parts of deionized water in parts by weight, and placing the materials into a stirrer to be uniformly mixed;
weighing 30 parts of glass fiber, putting into a stirrer, and fully mixing to form uniform and plastic pug;
thirdly, putting the pug obtained in the second step under a vacuum condition for aging for 15-25h;
and (IV) putting the aged pug into a horizontal bar reciprocating hydraulic extruder, extruding and molding to obtain an integral honeycomb desulfurization and denitrification catalyst, drying the integral honeycomb desulfurization and denitrification catalyst for 45 hours at room temperature, then putting the integral honeycomb desulfurization and denitrification catalyst into a drying box at 70 ℃ for drying for 4 hours, and after the quality is constant, putting the integral honeycomb desulfurization and denitrification catalyst into a calcining kiln, and respectively carrying out calcination at 250 ℃ and 450 ℃ for 4 hours.
Example 2
The pretreatment of the H-beta molecular sieve carrier comprises the following steps:
(1) Placing 100 parts of H-beta molecular sieve in a muffle furnace, heating to 600 ℃, roasting for 5 hours, and cooling to room temperature for later use;
(2) And (2) putting the carrier treated in the step (1) into a beaker, adding deionized water, 60 parts of nickel nitrate solution and 35 parts of nonmetal P, and uniformly stirring.
(3) And (3) placing the sample treated in the step (2) in a thermostat water bath kettle at 55 ℃ for soaking for 9h, transferring the sample into a drying box at 120 ℃ and drying for 14h.
(4) Placing the dried sample in the step (3) in a muffle furnace, roasting for 5 hours at 600 ℃, and cooling to room temperature to obtain a required sample;
(5) And (5) placing the sample obtained in the step (4) on a tablet machine, tabletting 7min under the pressure of 25MPa, and sieving the sample to 40 meshes for later use.
The preparation method of the coking flue gas desulfurization and denitrification catalyst comprises the following steps:
accurately weighing 6 parts of sesbania powder, 6 parts of polyoxyethylene, 60 parts of red mud, 110 parts of silica sol, 100 parts of pretreated carrier and 100 parts of deionized water in parts by weight, and placing the components into a stirrer to be uniformly mixed;
weighing 50 parts of ceramic fiber, putting into a stirrer, and fully mixing to form uniform and plastic pug;
thirdly, putting the pug obtained in the second step under a vacuum condition for ageing for 25 hours;
and (IV) putting the aged pug into a horizontal bar reciprocating hydraulic extruder, extruding and molding to obtain an integral honeycomb-shaped desulfurization and denitrification catalyst, drying the integral honeycomb-shaped desulfurization and denitrification catalyst for 55 hours at room temperature, then putting the integral honeycomb-shaped desulfurization and denitrification catalyst into a drying box at 90 ℃ for drying for 8 hours, and after the quality is constant, putting the integral honeycomb-shaped desulfurization and denitrification catalyst into a calcining kiln, and performing calcination at 350 ℃ and 600 ℃ respectively for 6 hours.
Example 3
The pretreatment of the H-beta molecular sieve carrier comprises the following steps:
(1) Placing 90 parts of H-beta molecular sieve in a muffle furnace, heating to 550 ℃, roasting for 4 hours, and cooling to room temperature for later use;
(2) And (2) putting the carrier treated in the step (1) into a beaker, adding deionized water, 40 parts of ferric nitrate solution and 20 parts of nonmetal auxiliary agent B, and uniformly stirring.
(3) And (3) placing the sample treated in the step (2) in a constant-temperature water bath kettle at 45 ℃ for soaking for 8h, transferring the sample into a drying box at 110 ℃ and drying for 13h.
(4) Placing the dried sample in the step (3) in a muffle furnace, roasting at 550 ℃ for 4h, and cooling to room temperature to obtain a required sample;
(5) And (5) placing the sample obtained in the step (4) on a tablet machine, tabletting 6 min under the pressure of 20MPa, and sieving the sample to 40 meshes for later use.
The preparation method of the coking flue gas desulfurization and denitrification catalyst comprises the following steps:
accurately weighing 3-6 parts of carboxymethyl cellulose, 2-6 parts of glass fiber, 55 parts of red mud, 90 parts of boehmite, 90 parts of pretreated carrier and 100 parts of deionized water according to parts by weight, and putting the mixture into a stirrer to be uniformly mixed;
weighing 45 parts of glass fiber, putting the glass fiber into a stirrer, and fully mixing to form uniform and plastic pug;
thirdly, putting the pug obtained in the second step under a vacuum condition for ageing for 20 hours;
and (IV) putting the aged pug into a horizontal bar reciprocating hydraulic extruder, extruding and molding to obtain an integral honeycomb desulfurization and denitrification catalyst, drying the integral honeycomb desulfurization and denitrification catalyst for 50 hours at room temperature, then putting the integral honeycomb desulfurization and denitrification catalyst into a drying box at 80 ℃ for drying for 7 hours, and after the quality is constant, putting the integral honeycomb desulfurization and denitrification catalyst into a calcining kiln, and respectively carrying out calcination at 300 ℃ and 500 ℃ for 6 hours.
Example 4
The pretreatment of the H-beta molecular sieve carrier comprises the following steps:
(1) Placing 80 parts of H-beta molecular sieve in a muffle furnace, heating to 500 ℃, roasting for 4 hours, and cooling to room temperature for later use;
(2) Putting the carrier treated in the step (1) into a beaker, adding deionized water, 50 parts of chromium nitrate solution and 25 parts of metal auxiliary agent Ca, and uniformly stirring;
(3) Placing the sample treated in the step (2) in a constant-temperature water bath kettle at 45 ℃ for soaking for 8 hours, transferring the sample into a drying box at 100 ℃, and drying for 12 hours;
(4) Placing the dried sample in the step (3) in a muffle furnace, roasting for 4 hours at 500-600 ℃, and cooling to room temperature to obtain a required sample;
(5) And (3) placing the sample obtained in the step (4) on a tablet machine, tabletting 4 min under the pressure of 20MPa, and sieving the sample to 20 meshes for later use.
The preparation method of the coking flue gas desulfurization and denitrification catalyst comprises the following steps:
accurately weighing the 5 parts of polyvinyl alcohol, 3 parts of polyoxyethylene, 46 parts of red mud, 90 parts of silica sol, 80 parts of pretreated carrier and 100 parts of deionized water in parts by weight, and placing the mixture into a stirrer to be uniformly mixed;
weighing 35 parts of ceramic fiber, putting into a stirrer, and fully mixing to form uniform and plastic pug;
thirdly, putting the pug obtained in the second step under a vacuum condition for ageing for 20 hours;
and (IV) putting the aged pug into a horizontal bar reciprocating hydraulic extruder, extruding and molding to obtain an integral honeycomb desulfurization and denitrification catalyst, drying the integral honeycomb desulfurization and denitrification catalyst for 50 hours at room temperature, then putting the integral honeycomb desulfurization and denitrification catalyst into a drying box at 80 ℃ for drying for 6 hours, and after the quality is constant, putting the integral honeycomb desulfurization and denitrification catalyst into a calcining kiln, and respectively carrying out calcination at 300 ℃ and 500 ℃ for 5 hours.
Example 5
The pretreatment of the H-beta molecular sieve carrier comprises the following steps:
(1) Placing 90 parts of H-beta molecular sieve in a muffle furnace, heating to 500 ℃, roasting for 4 hours, and cooling to room temperature for later use;
(2) Putting the carrier treated in the step (1) into a beaker, adding deionized water, 50 parts of cobalt nitrate solution and 25 parts of metal additive La, and uniformly stirring;
(3) Placing the sample treated in the step (2) in a constant-temperature water bath kettle at 45 ℃ for soaking for 8h, transferring the sample into a drying box at 110 ℃, and drying for 13h;
(4) Placing the dried sample in the step (3) in a muffle furnace, roasting at 550 ℃ for 4h, and cooling to room temperature to obtain a required sample;
(5) And (5) placing the sample obtained in the step (4) on a tablet machine, tabletting 6 min under the pressure of 20MPa, and sieving the sample to 30 meshes for later use.
The preparation method of the coking flue gas desulfurization and denitrification catalyst comprises the following steps:
accurately weighing 4 parts of polyvinyl alcohol, 4 parts of polyethylene oxide, 50 parts of red mud, 100 parts of boehmite, 90 parts of pretreated carrier and 100 parts of deionized water in parts by weight, and placing the materials into a stirrer to be uniformly mixed;
weighing 40 parts of ceramic fiber, putting into a stirrer, and fully mixing to form uniform and plastic pug;
thirdly, putting the pug obtained in the second step under a vacuum condition for ageing for 20 hours;
and (IV) putting the aged pug into a horizontal bar reciprocating hydraulic extruder, extruding and molding to obtain an integral honeycomb desulfurization and denitrification catalyst, drying the integral honeycomb desulfurization and denitrification catalyst for 50 hours at room temperature, then putting the integral honeycomb desulfurization and denitrification catalyst into a drying box at 85 ℃ for drying for 7 hours, and after the quality is constant, putting the integral honeycomb desulfurization and denitrification catalyst into a calcining kiln, and respectively carrying out calcination at 250 ℃ and 600 ℃ for 6 hours.
Comparative example 1
The difference compared to example 3 is that no auxiliary agent was added in the pretreatment step (2).
Comparative example 2
The difference from example 3 is that in the pretreatment step (2), the active metal component put in is alumina.
Comparative example 3
Compared with the example 3, the difference is that in the step (IV) of the preparation method of the coking flue gas desulfurization and denitrification catalyst, a flat plate type desulfurization and denitrification catalyst is prepared.
Comparative example 4
Compared with the embodiment 3, the difference is that 10 to 20 parts of carboxymethyl cellulose is added in the step (I) of the preparation method of the coking flue gas desulfurization and denitrification catalyst.
The above examples 1-5 and comparative examples 1-4 were placed: 2500ppmCO,1000ppmSO 2 The results of the experiment conducted in a simulated flue gas containing 500ppm NO and nitrogen as the balance gas are shown in Table 1.
TABLE 1
As shown in Table 1, in examples 1 to 5, the desulfurization and denitrification performance was the most excellent for the raw materials used in example 3 in each ratio.
Comparative example 1 compared with examples 1-5, no adjuvant was added in the pretreatment step (2); the nonmetal auxiliary agent modulates the physical texture performance and surface chemical property of the catalyst, improves the dispersibility of active metal and the synergistic effect among the components, and increases the surface active phase of the catalyst; the metal auxiliary agent can effectively adjust the acid-base sites on the surface of the carrier and inhibit the agglomeration of active species on the surface of the catalyst; the metal auxiliary agent and the carrier form a mixed oxide junctionThe structure weakens the interaction of the active component and the carrier, increases the dispersion of the active phase on the surface of the catalyst, and improves the desulfurization and denitrification activity of the catalyst, namely SO is caused after no addition of the auxiliary agent 2 The conversion and NO conversion decrease.
Compared with the examples 1 to 5, the difference of the comparative example 2 is that in the pretreatment step (2), when active metal ions are loaded in the molecular sieve, the acid-base sites can be changed, the denitration activity of the catalyst is improved, the alumina is used as an irregular carrier, the surface property and the microstructure have larger influence on the porosity of the molecular sieve, the performance of the catalyst is greatly influenced, and the NO conversion rate is reduced.
Comparative example 3 is different from examples 1 to 5 in that a flat-plate type desulfurization and denitrification catalyst was prepared; compared with the flat plate type desulfurization and denitrification catalyst, the honeycomb type catalyst can be applied to both high ash and low ash conditions, and has the advantages of large opening area, small pressure drop, difficult blockage, wide reaction temperature range, high activity, strong selectivity and the like, namely, the flat plate type desulfurization and denitrification catalyst is influenced by more influencing factors and influences the desulfurization and denitrification conversion rate.
Comparative example 4 is different from examples 1 to 5 in that 10 to 20 parts of carboxymethyl cellulose is added, and the carboxymethyl cellulose is completely oxidized at about 300 ℃ to generate H 2 O and CO 2 However, when the amount of the additive exceeds 3%, the adhesive force between the powders is too strong, the powders are not easily distributed uniformly, the molding process is difficult, the plasticity is poor, the extrusion molding is not facilitated, and the final use is affected.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A coking flue gas desulfurization and denitrification catalyst is characterized by comprising 30-60 parts of active metal, 15-35 parts of catalytic promoter, 70-100 parts of carrier and 90-120 parts of forming promoter by weight;
the active metal is at least one of VIB, VIIB and VIII group metals;
the auxiliary agent is non-metal auxiliary agent P, B, F or one or more of metal auxiliary agents Mg, ca, la and Ce;
the carrier is an H-beta molecular sieve, and the H-beta molecular sieve is pretreated;
the pretreatment mainly comprises the following steps:
(1) Placing the H-beta molecular sieve in a muffle furnace, heating to 400-600 ℃, roasting for 3-5H, and cooling to room temperature for later use;
(2) Putting the carrier treated in the step (1) into a beaker, adding deionized water, an active metal salt solution and an auxiliary agent, and uniformly stirring;
(3) Placing the sample treated in the step (2) in a constant-temperature water bath kettle at 35-55 ℃ for soaking for 7-9h, transferring the sample into a drying box at 100-120 ℃ and drying for 11-14h;
(4) And (4) placing the dried sample in the step (3) in a muffle furnace, roasting at 500-600 ℃ for 3-5h, and cooling to room temperature to obtain the required sample.
2. The coking flue gas desulfurization and denitrification catalyst of claim 1, wherein the forming aid comprises, by weight, 3-6 parts of an organic binder, 2-6 parts of a plasticizer, 30-50 parts of a structural aid, 40-60 parts of red mud and 80-110 parts of an inorganic binder;
the organic adhesive is at least one of carboxymethyl cellulose, sesbania powder and polyvinyl alcohol;
the plasticizer is polyoxyethylene or polyvinyl chloride;
the structural auxiliary agent is glass fiber or ceramic fiber;
the inorganic binder is at least one of boehmite, silica sol and alumina sol.
3. The coking flue gas desulfurization and denitrification catalyst according to claim 1, wherein the carrier treated in the step (1) is placed in a beaker, deionized water is added while stirring until no excess deionized water is separated out, and the amount of the deionized water used is the same as that in the step (2).
4. A coking flue gas desulfurization and denitrification catalyst in accordance with claim 1 wherein the active metal is specifically at least one of Co, ni, mn, cr, fe.
5. The coking flue gas desulfurization and denitrification catalyst of claim 1, wherein the mass ratio of the active metal salt solution to the molecular sieve is (0.2-0.5): 1.
6. the coking flue gas desulfurization and denitrification catalyst of claim 1, wherein the H-beta molecular sieve has a specific surface area of 400-500m 2 (ii)/g, pore diameter is 0.3-0.5nm.
7. The coking flue gas desulfurization and denitrification catalyst of claim 1, wherein the sample obtained in the step (4) is placed on a tabletting machine, tabletted for 4-7min under a pressure of 15-25MPa, and sieved to 20-40 mesh for later use.
8. The method for preparing a desulfurization and denitrification catalyst for a coking flue gas as claimed in any one of claims 1 to 7, comprising the steps of:
accurately weighing 3-6 parts of the organic binder, 2-6 parts of the plasticizer, 40-60 parts of red mud, 80-110 parts of the inorganic binder, 70-100 parts of the pretreated carrier and 100 parts of deionized water by weight, and placing the mixture into a stirrer to be uniformly mixed;
weighing 30-50 parts of structural auxiliary agent, putting into a stirrer, and fully mixing to form uniform and plastic pug;
thirdly, putting the pug obtained in the second step under a vacuum condition for ageing for 15-25h;
and (IV) putting the aged pug into a horizontal bar reciprocating hydraulic extruder, extruding and molding to obtain an integral honeycomb desulfurization and denitrification catalyst, and calcining to obtain the coking flue gas desulfurization and denitrification catalyst.
9. The method for preparing a desulfurization and denitrification catalyst for coking flue gas according to claim 8, wherein in the step (IV), the calcination treatment process is: the monolithic honeycomb desulfurization and denitrification catalyst is dried for 45-55 hours at room temperature, then is placed in a drying box at 70-90 ℃ for drying for 4-8 hours, and is placed in a calcining kiln for two-section calcining after the quality is constant.
10. The method for preparing a desulfurization and denitrification catalyst for coking flue gas according to claim 9, wherein the two-stage calcination is carried out at 250-350 ℃ and 450-600 ℃ respectively, and the calcination time is 4-6h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116832856A (en) * | 2023-07-10 | 2023-10-03 | 昆明贵研催化剂有限责任公司 | Sulfur capture catalyst for diesel engine and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437608A (en) * | 2014-10-09 | 2015-03-25 | 南开大学 | Catalyst for performing selective catalytic reduction on nitrogen oxide by ammonia |
| CN108421558A (en) * | 2018-04-04 | 2018-08-21 | 武汉理工大学 | A kind of bar shaped manganese-based catalyst and preparation method thereof for NO catalysis oxidations |
| CN110813072A (en) * | 2019-12-03 | 2020-02-21 | 西南化工研究设计院有限公司 | Novel integrated material for flue gas desulfurization, denitrification and CO removal, and preparation and application thereof |
| CN112439423A (en) * | 2019-08-30 | 2021-03-05 | 大连海事大学 | Sulfur-resistant NO oxidation regular structure catalyst and preparation method and application thereof |
| CN112547129A (en) * | 2020-12-23 | 2021-03-26 | 天津水泥工业设计研究院有限公司 | Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method and application thereof |
| CN113731498A (en) * | 2021-09-16 | 2021-12-03 | 山东中移能节能环保科技股份有限公司 | Coke oven flue gas denitration agent catalyst and preparation method thereof |
| CN114682297A (en) * | 2020-12-30 | 2022-07-01 | 中国石油大学(北京) | Low-temperature denitration catalyst and preparation method and application thereof |
-
2022
- 2022-12-21 CN CN202211647900.6A patent/CN115869992A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437608A (en) * | 2014-10-09 | 2015-03-25 | 南开大学 | Catalyst for performing selective catalytic reduction on nitrogen oxide by ammonia |
| CN108421558A (en) * | 2018-04-04 | 2018-08-21 | 武汉理工大学 | A kind of bar shaped manganese-based catalyst and preparation method thereof for NO catalysis oxidations |
| CN112439423A (en) * | 2019-08-30 | 2021-03-05 | 大连海事大学 | Sulfur-resistant NO oxidation regular structure catalyst and preparation method and application thereof |
| CN110813072A (en) * | 2019-12-03 | 2020-02-21 | 西南化工研究设计院有限公司 | Novel integrated material for flue gas desulfurization, denitrification and CO removal, and preparation and application thereof |
| CN112547129A (en) * | 2020-12-23 | 2021-03-26 | 天津水泥工业设计研究院有限公司 | Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method and application thereof |
| CN114682297A (en) * | 2020-12-30 | 2022-07-01 | 中国石油大学(北京) | Low-temperature denitration catalyst and preparation method and application thereof |
| CN113731498A (en) * | 2021-09-16 | 2021-12-03 | 山东中移能节能环保科技股份有限公司 | Coke oven flue gas denitration agent catalyst and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 庞子涛: "铁基氧化物同时脱硫脱硝催化剂的制备与性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 09, 15 September 2019 (2019-09-15), pages 014 - 715 * |
| 庞子涛等: "负载型铁铬催化剂同时脱硫脱硝性能", 《环境科学与技术》, vol. 42, no. 12, 15 December 2019 (2019-12-15), pages 112 - 117 * |
| 徐丽婷等: "Mg掺杂改性γ -Fe2O3催化剂NH3-SCR脱硝特性", 《煤炭学报》, vol. 42, no. 7, 15 July 2017 (2017-07-15), pages 1884 - 1891 * |
| 陈邱谆: "蜂窝状赤泥催化剂的成型制备及脱硝性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 12, 15 December 2021 (2021-12-15), pages 014 - 405 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116832856A (en) * | 2023-07-10 | 2023-10-03 | 昆明贵研催化剂有限责任公司 | Sulfur capture catalyst for diesel engine and preparation method thereof |
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