CN107413393A - A kind of wear-resistant composite denitration catalyst and preparation method for glass furnace - Google Patents

A kind of wear-resistant composite denitration catalyst and preparation method for glass furnace Download PDF

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Publication number
CN107413393A
CN107413393A CN201710488054.0A CN201710488054A CN107413393A CN 107413393 A CN107413393 A CN 107413393A CN 201710488054 A CN201710488054 A CN 201710488054A CN 107413393 A CN107413393 A CN 107413393A
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wear
catalyst
resisting
glass furnace
resistant ceramic
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吴道君
李军营
杨晓波
皮镜
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Hubei Qunyouchangwu Environmental Protection Technology Co ltd
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Hubei Shenwu Thermal Energy Technology Co Ltd
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Abstract

The present invention is a kind of wear-resistant ceramic composite denitration catalyst for glass furnace and preparation method thereof, it is characterized in that termination position is wear-resisting Extruded Monolithic Celluar Ceramics, described main body section is wear-resisting cellular catalyst, both are combined with each other by being bonded hardening mud layer adhesion one in surrounding using stainless steel case nesting.It is mainly used in the denitrification apparatus of glass furnace, is applicable to the denitration of 250 ~ 400 DEG C wide temperature high-dust flue gas, termination position Extruded Monolithic Celluar Ceramics abrasion resistance properties are significantly better than traditional cellular catalyst, and overall denitration performance does not decline.

Description

A kind of wear-resistant composite denitration catalyst and preparation method for glass furnace
Technical field
The invention belongs to industrial energy saving, emission abatement device technical field, and in particular to a kind of for the wear-resisting of glass furnace Damage Ceramic Composite denitrating catalyst and preparation method thereof.
Background technology
Nitrogen oxides in air（NOx）A kind of common atmosphere pollution, it can not only cause acid rain, photochemical fog, Earth's surface water eutrophication etc. destroys a series of problems of ecological environment, while also entail dangers to human health.Therefore, control in air NOx discharge causes the concern in the whole world, and China is also classified as the emphasis in current atmospheric environment protection.
Research finds NO during fuel combustionxGeneration：First, nitrogen during burning in air is oxidized and generated at high temperature Nitrogen oxides, second, the nitrogen that the nitrogen-containing compound in fuel decomposites at high temperature is oxidized to nitrogen oxides, glassware life The flue gas discharged during production contains 3000-7000ppm nitrogen oxides.Its discharge capacity is only second to thermal power plant, row Enter one of source of atmospheric pollution, China's glass furnace also generates substantial amounts of NO while promoting economic developmentx。
Reduce NOxDischarge has two approach of denitrating flue gas after Combustion Process Control and burning.In actual production, low NOx combustions Burning technology efficiency is low, and mainly uses gas denitrifying technology.At present, the SCR denitration technology in gas denitrifying technology has denitration The advantages that rate is high (can be more than 90%), and selectivity is good, and technology maturation is reliable, turn into the main flow of glass furnace denitration.
The part of most critical is catalyst in SCR denitration system, and glass furnace fume dust content is higher, is flown in flue gas Ash particle rapid shock catalyst duct, in the lower flue gas that works long hours abrasion of the flying dust to catalyst catalyst mould mainly occurs The end portion of block, corresponding end wear is the most serious, and growth over time, and catalyst module can be shorter and shorter, makes The service life of catalyst is greatly reduced and further occurs and cavity and cave in, reduce denitration efficiency.
Although traditional honeycomb type denitrification catalyst is handled using the termination hardening bath of impregnation of phosphoric acid aluminum dihydrogen（Publication number： CN 103316717 A）, but it is also more serious using wearing under the flue gas of high dust-laden, have a strong impact on service life；Or in material Antiwear additive SiC is added in material formula（Publication number：CN 106311301 A）, but due to SiC powder material and in catalyst calcination At a temperature of can not be firmly combined with, still have that compressive resistance is not high, used under the flue gas of high dust-laden, denitrating catalyst also can be gradual It is worn.
Abrasion and flue gas flow rate and dust concentration, catalyst abrasion position etc. have certain relation.Therefore, invention is a kind of Thus glass furnace is produced with the technical barrier that wear-resistant composite denitration catalyst is that this area is badly in need of solving at this stage, the present invention It is raw.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of wear-resistant ceramic composite denitration for glass furnace and urged Agent and preparation method thereof.It is not high to solve existing denitrating catalyst anti-wear performance, decay resistance, it is easily long-pending during use The technical problems such as ash blocks, the small heat exchange efficiency of specific surface area is low, service life is short.In glass furnace denitration device, with one kind Wear-resistant ceramic composite can replace existing denitrating catalyst termination hardening position, by the simple cleanings of Bu Fan factories again It is raw, the cost effective cleaning and regeneration of inactivation denitrating catalyst can be realized.
To achieve these goals, the technical solution used in the present invention is：A kind of wear-resistant pottery for glass furnace Porcelain composite denitration catalyst and preparation method thereof, wear-resistant ceramic composite denitration catalyst include termination position, main body section, glued Connect hardening mud layer, stainless steel case connection combines；Described termination position is wear-resisting Extruded Monolithic Celluar Ceramics, and there is positioning lower end Raised line；Described main body section is wear-resisting cellular catalyst, and there is detent upper end；The lower end at the termination position and main body The upper end at position is equipped with stainless steel case by being bonded hardening mud layer adhesion one, the bonding hardening mud layer surrounding.
Preferably, the bonding hardening mud layer uses aluminium dihydrogen phosphate, the immersion mixing of lucium active component Formed.
Preferably, the termination position uses wear-resisting Extruded Monolithic Celluar Ceramics, including step is produced by below：
1）Wear-resisting Extruded Monolithic Celluar Ceramics include inorganic powder and additive, and the additive includes solid-state adhesion agent, lubricant, Organic plasticising NMF；
Inorganic powder percetage by weight as shared by each raw material is：Andalusite 10 ~ 50%, cordierite 10 ~ 30%, spodumene 10 ~ 30%th, white fused alumina 5 ~ 10%, potassium feldspar 1 ~ 10%, kaolin 1 ~ 10%, flint clay 5 ~ 35%；The weight of above-mentioned inorganic powder is with 100 parts Meter, the agent of addition solid-state adhesion is 3 ~ 7 parts, 2 ~ 6 parts of lubricant, 0.5 ~ 2 part of organic plasticising NMF.
2）The preparation of wear-resisting Extruded Monolithic Celluar Ceramics：Ball milling, kneading, old obtained pug are molded by extruder, obtained To honeycomb ceramics base substrate；Hot-air kiln dryness finalization is placed on after microwave is shaped；Burnt till by 1300 ~ 1350 DEG C, obtain termination The honeycomb ceramic heat accumulator material at position.
Preferably, described wear-resisting Extruded Monolithic Celluar Ceramics are placed on sizing in heated-air drying kiln and dried, initial sizing temperature 65 DEG C of degree, 6 ~ 12h of drying time；The power of microwave sizing microwave oven is 5 ~ 10kW, and frequency is 2450MHz ± 50MHz.
The preparation of wear-resisting Extruded Monolithic Celluar Ceramics：Ball milling, kneading, old obtained pug are molded by extruder, obtained Honeycomb ceramics base substrate；Hot-air kiln dryness finalization is placed on after microwave is shaped；Burnt till by 1300 ~ 1350 DEG C, obtain end head The honeycomb ceramic heat accumulator material of position.
Preferably, solid-state adhesion agent is HPMC, CMC one or more mixing in the wear-resisting Extruded Monolithic Celluar Ceramics Thing.Organic lubricant is vegetable oil, stearic acid, one or more mixtures of synthetic motor oil.Organic plasticising NMF be PEO, PVA one or more mixtures.
Preferably, the wear-resisting cellular catalyst, its production stage are as follows：
1）Wear-resisting cellular catalyst includes inorganic powder and additive, and the additive includes solid-state adhesion agent, lubricant, Organic plasticising NMF；
Inorganic powder percetage by weight as shared by each raw material is：Titanium dioxide 70-90%, montmorillonite 1-15%, rare earth mix Compound 1-10%, glass fibre 1-5%, wood pulp cotton 1-5%；The weight of above-mentioned inorganic powder adds solid-state adhesion in terms of 100 parts Agent is 0.5 ~ 5 part, 0.5 ~ 5 part of lubricant, 0.5 ~ 2 part of organic plasticising NMF.
2）The preparation of wear-resisting cellular catalyst：Kneading will be stirred, the vacuum equipped with mould is passed through in old, pre-filtering Extruder shaping extrusion, is made the wet base of catalyst；Wherein old more than 24h；Pre-filtering uses specification 1 × 4mm or 0.8 × 3mm Stainless steel filtering net；By hot-air kiln dryness finalization, then by 600 DEG C of calcinings, the wear-resisting honeycomb fashion for obtaining main body section is urged Agent.
Preferably, the extrusion pressure of the vacuum-extruder is 3 ~ 6MPa, 35 DEG C of extrusion temperature ＜, extrusion vacuum- 0.09MPa。
Preferably, the solid-state adhesion agent is CMC, the organic lubricant is stearic acid, organic plasticising moisturizing Agent is PEO.
The wear-resistant ceramic composite denitration catalyst of the present invention, is mainly used in the denitrification apparatus of glass furnace, applicable In the denitration of 250 ~ 400 DEG C wide temperature high-dust flue gas, termination position Extruded Monolithic Celluar Ceramics abrasion resistance properties are significantly better than tradition Cellular catalyst, and overall denitration performance does not decline.Because termination position abrasion resistance properties are good, pass through the letter of Bu Fan factories Single cleaning and regeneration, the cost effective cleaning and regeneration of inactivation denitrating catalyst can be realized.Ceramic Composite denitrating catalyst of the present invention Have the advantages that cost is low, service life is long, catalytic activity is high, wearability is good.It can be additionally used in the industries such as electric power, metallurgy, petrochemical industry Denitrating flue gas, have wide range of applications, environment protection significance is great.
Brief description of the drawings
Structural representation when being perpendicular positioning of the present invention shown in Fig. 1.
Embodiment
For a better understanding of the present invention, with reference to embodiment, technical scheme is made further Specific description.
As shown in figure 1, a kind of wear-resistant ceramic composite denitration catalyst for glass furnace and preparation method thereof, wear-resisting Damaging Ceramic Composite denitrating catalyst includes termination position 1, main body section 2, bonding hardening mud layer 3, the connection combination of stainless steel case 4 Form, its appearance and size is 150mm × 150mm, 700 ~ 800mm of total height, termination position height 45mm.Termination position 1 is resistance to Extruded Monolithic Celluar Ceramics are ground, there is positioning convex strip 11 lower end.Main body section 2 is wear-resisting cellular catalyst, and there is detent its upper end 21.Both can prevent that airflow hole inconsistent phenomenon occurs between termination position 1 and main body section 2 with accurate positioning, hard by being bonded Change the adhesion of mud layer 3 one, and be combined with each other in surrounding using the nesting of stainless steel case 4.
Termination position 1 is as follows using wear-resisting Extruded Monolithic Celluar Ceramics production stage：
1）Inorganic powder percetage by weight as shared by each raw material is in wear-resisting Extruded Monolithic Celluar Ceramics：Andalusite 15%, cordierite 15%, Spodumene 15%, white fused alumina 15%, potassium feldspar 10%, kaolin 10%, flint clay 20%；The weight of above-mentioned inorganic powder is with 100 parts Meter, the agent of addition solid-state adhesion is 3.5 parts, 5 parts of lubricant, 1 part of organic plasticising NMF.
2）The preparation of wear-resisting Extruded Monolithic Celluar Ceramics：Ball milling, kneading, old obtained pug are molded by extruder, obtained To honeycomb ceramics base substrate；Hot-air kiln dryness finalization is placed on after microwave is shaped；Burnt till by 1300 ~ 1350 DEG C, obtain termination The honeycomb ceramic heat accumulator material at position.Described ceramic honey comb production stage：It is placed on sizing in heated-air drying kiln and dries, just 65 DEG C of beginning setting temperature, 6 ~ 12h of drying time；The power of microwave sizing microwave oven be 5kW, frequency for 2450MHz ± 50MHz；Solid-state adhesion agent HPMC is 3.5 parts；Organic lubricant vegetable oil is 4 parts；Organic plasticising NMF PEO is 1 part.Through surveying Examination, the compression strength of honeycomb ceramic heat accumulator is 26~29MPa, bulk density is 2.1~2.2g/cm3, wearability be 7.6cm3, meet performance requirement of the glass furnace with wear-resistant composite denitration catalyst termination position.
Main body section 2 is as follows using wear-resisting cellular catalyst production stage：
1）Wear-resisting cellular catalyst includes inorganic powder and additive, and the additive includes solid-state adhesion agent, lubricant, Organic plasticising NMF；
Inorganic powder percetage by weight as shared by each raw material is：Titanium dioxide 75%, montmorillonite 10%, lucium 10%th, glass fibre 2.5%, wood pulp cotton 2.5%；For the weight of above-mentioned inorganic powder in terms of 100 parts, it is 1 to add solid-state adhesion agent Part, 1 part of lubricant, 1 part of organic plasticising NMF.Solid-state adhesion agent is CMC, and organic lubricant is stearic acid, and organic plasticising is protected Humectant is PEO.
2）The preparation of wear-resisting cellular catalyst：Stirring is mediated, old, pre-filtering passes through the vacuum equipped with mould Extruder shaping extrusion, is made the wet base of catalyst；By hot-air kiln dryness finalization；By 600 DEG C of calcinings, main body section is obtained Wear-resisting cellular catalyst.The old time is more than 24h；Pre-filtering is filtered using specification 1 × 4mm or 0.8 × 3mm stainless steel Net；The extrusion pressure of vacuum-extruder is 3 ~ 6MPa, 35 DEG C of extrusion temperature ＜, extrudes vacuum -0.09MPa.After tested, it is wear-resisting The compression strength of cellular catalyst is 4~5MPa, 0.05 ~ 0.10 %/kg of hardening abrasion, it is contemplated that the longevity of catalyst is 2 ~ 3 Year, meet performance requirement of the glass furnace with wear-resistant composite denitration catalyst body position.
Finally it is pointed out that above embodiment is only the more representational example of the present invention.Obviously, it is of the invention Above-mentioned embodiment is not limited to, there can also be many deformations.Every technical spirit according to the present invention specific reality to more than Any simple modification, equivalent change and modification that the mode of applying is made, it is considered as belonging to protection scope of the present invention.

Claims (9)

1. a kind of wear-resistant ceramic composite denitration catalyst for glass furnace and preparation method thereof, wear-resistant ceramic is compound de- Denox catalyst includes termination position, main body section, bonding hardens mud layer, stainless steel case connection combines, it is characterised in that Described termination position is wear-resisting Extruded Monolithic Celluar Ceramics, and there is positioning convex strip lower end, and described main body section is that wear-resisting honeycomb fashion is urged Agent, upper end have detent, the lower end at the termination position and the upper end of main body section to harden mud layer adhesion by being bonded One, the bonding hardening mud layer surrounding are equipped with stainless steel case.
It is 2. according to claim 1 a kind of for the wear-resistant ceramic composite denitration catalyst of glass furnace and its preparation side Method, it is characterised in that the bonding hardening mud layer is mixed to form using aluminium dihydrogen phosphate, the immersion of lucium active component.
It is 3. according to claim 1 a kind of for the wear-resistant ceramic composite denitration catalyst of glass furnace and its preparation side Method, it is characterised in that the wear-resisting Extruded Monolithic Celluar Ceramics, including step is produced by below：
1）Wear-resisting Extruded Monolithic Celluar Ceramics include inorganic powder and additive, and the additive includes solid-state adhesion agent, lubricant, Organic plasticising NMF；
Inorganic powder percetage by weight as shared by each raw material is：Andalusite 10 ~ 50%, cordierite 10 ~ 30%, spodumene 10 ~ 30%th, white fused alumina 5 ~ 10%, potassium feldspar 1 ~ 10%, kaolin 1 ~ 10%, flint clay 5 ~ 35%；The weight of above-mentioned inorganic powder is with 100 parts Meter, the agent of addition solid-state adhesion is 3 ~ 7 parts, 2 ~ 6 parts of lubricant, 0.5 ~ 2 part of organic plasticising NMF;
2）The preparation of wear-resisting Extruded Monolithic Celluar Ceramics：Ball milling, kneading, old obtained pug are molded by extruder, obtain honeybee Nest body base substrate；Hot-air kiln dryness finalization and drying are placed on after microwave is shaped；Burn till, held by 1300 ~ 1350 DEG C The honeycomb ceramic heat accumulator material of head position.
It is 4. described a kind of for the wear-resistant ceramic composite denitration catalyst of glass furnace and its preparation according to claim 1 or 3 Method, it is characterised in that described wear-resisting Extruded Monolithic Celluar Ceramics are placed on sizing in heated-air drying kiln and dried, initial setting temperature 65 DEG C, 6 ~ 12h of drying time；The power of microwave sizing microwave oven is 5 ~ 10kW, and frequency is 2450MHz ± 50MHz.
It is 5. according to claim 3 a kind of for the wear-resistant ceramic composite denitration catalyst of glass furnace and its preparation side Method, it is characterised in that solid-state adhesion agent is HPMC, CMC one or more mixtures, and the organic lubricant is vegetable oil, firmly One or more mixtures of resin acid, synthetic motor oil；Organic plasticising NMF is PEO, PVA one or more mixing Thing.
It is 6. a kind of for the wear-resistant ceramic composite denitration catalyst of glass furnace and its preparation side according to claim 1 Method, it is characterised in that the wear-resisting cellular catalyst, including step is produced by below：
1）Wear-resisting cellular catalyst includes inorganic powder and additive, and the additive includes solid-state adhesion agent, lubricant, Organic plasticising NMF；
Inorganic powder percetage by weight as shared by each raw material is：Titanium dioxide 70-90%, montmorillonite 1-15%, rare earth mix Compound 1-10%, glass fibre 1-5%, wood pulp cotton 1-5%；The weight of above-mentioned inorganic powder adds solid-state adhesion in terms of 100 parts Agent is 0.5 ~ 5 part, 0.5 ~ 5 part of lubricant, 0.5 ~ 2 part of organic plasticising NMF;
2）The preparation of wear-resisting cellular catalyst：Stirring is mediated, old, pre-filtering is passed through equipped with the shaping of mould vacuum-extruder Extrusion, the wet base of catalyst is made；By hot-air kiln dryness finalization；By 600 DEG C of calcinings, the wear-resisting honeycomb of main body section is obtained Formula catalyst.
It is 7. a kind of for the wear-resistant ceramic composite denitration catalyst of glass furnace and its preparation side according to claim 6 Method, it is characterised in that the wet base of catalyst, which is made, needs old more than 24h；Pre-filtering is stainless using specification 1 × 4mm's or 0.8 × 3mm Steel filter screen.
It is 8. according to claim 6 a kind of for the wear-resistant ceramic composite denitration catalyst of glass furnace and its preparation side Method, the extrusion pressure of vacuum-extruder described in its feature are 3 ~ 6MPa, 35 DEG C of extrusion temperature ＜, extrude vacuum -0.09MPa.
It is 9. according to claim 6 a kind of for the wear-resistant ceramic composite denitration catalyst of glass furnace and its preparation side Method, it is characterised in that the solid-state adhesion agent is CMC, and the organic lubricant is stearic acid, and organic plasticising NMF is PEO。
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