CN109160803A - Desulfurizing and denitrifying process proppant and preparation method thereof - Google Patents
Desulfurizing and denitrifying process proppant and preparation method thereof Download PDFInfo
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- CN109160803A CN109160803A CN201811172447.1A CN201811172447A CN109160803A CN 109160803 A CN109160803 A CN 109160803A CN 201811172447 A CN201811172447 A CN 201811172447A CN 109160803 A CN109160803 A CN 109160803A
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
- C04B38/0009—Honeycomb structures characterised by features relating to the cell walls, e.g. wall thickness or distribution of pores in the walls
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The present invention provides a kind of desulphurization denitration proppant, and raw material includes the component of following parts by weight: 50~60 parts of white fused alumina, γ-Al2O35~10 parts, 5~10 parts of magnesium aluminate spinel, 0.5~2 part of neodymia, 3~6 parts of polymethyl methacrylate.First by γ-Al when preparation2O3, magnesium aluminate spinel, neodymia premix uniformly, add polymethyl methacrylate and be uniformly mixed, be finally uniformly mixed it with white fused alumina, dry, sintering is made after green body.The present invention passes through white fused alumina, γ-Al2O3, magnesium aluminate spinel, neodymia, polymethyl methacrylate rational proportion, and by premix, mixing, base, drying, sintering and etc. obtained dense form proppant, its intensity is high, impact resistance, acid resistance are good, long service life, it is able to extend the replacement cycle of proppant in coke oven flue gas treatment process, reduces operating cost.
Description
Technical field
The present invention relates to industrial waste gas processing techniques, and in particular to desulphurization denitration proppant, while being related to its preparation side
Method.
Background technique
SO2, NOx be to form one of main matter of acid rain, caused by atmosphere pollution and acid rain problem get worse, to people
Class health and ecosystem harm are serious, SO2, NOx pollution have become restrict China's sustainable development of socio-economy it is important
Factor.It is detected according to environmental protection administration, particulate matter, sulfur dioxide, benzo (a) pyrrole, nitrogen oxides that domestic existing coke oven is discharged
Concentration be not able to satisfy existing " the coking chemistry emission of industrial pollutants standard " GB16172-2012 of country mostly.According to the mark
Newly-built enterprise and 1 Qi existing enterprise January in 2015 from alignment request on October 1st, 2012, the granular material discharged concentration of coke oven chimney
30mg/Nm3, sulfur dioxide 50mg/Nm3, nitrogen oxides 500mg/Nm3, benzo (a) pyrrole 0.3ug/Nm3；Special limit value is particle
Object concentration of emission 15mg/Nm3, sulfur dioxide 30mg/Nm3, nitrogen oxides 150mg/Nm3, benzo (a) pyrrole 0.3ug/Nm3, herein
Under background, develops and coking industry economy, feasible desulfurizing and denitrifying process technology is suitble to be industry development inexorable trends, meet country
The demand of environmental protection.Existing desulfurization technology is broadly divided into wet process of FGD, dry flue gas desulphurization and semidry method by process characteristic
Flue gas desulfurization；The main now industrial widely applied technology of denitration is SCR (selective catalytic reduction) and SNCR (selectivity
Noncatalytic reduction), wherein SNCR denitration needs high-temperature area, and coke oven production process is difficult to realize, while SNCR method is in furnace
Thorax internal spray reducing agent can impact coke oven production technology, and the production technology characteristic of coke oven does not allow in coke oven
Inside carry out gametic fertility, therefore SNCR method be not suitable for coke oven flue gas denitration, therefore coke oven flue gas denitration use SCR skill
Art.But current coke oven flue gas desulphurization denitration still has much room for improvement in comprehensive treatment, especially anti-to wherein adsorbent support agent
It needs further to study in terms of impact property, acidresistant property.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of shock resistance, the good processing coke oven of corrosion resistance
The proppant of flue gas.
The technical solution of the present invention is to provide a kind of desulfurizing and denitrifying process proppant, raw material includes following parts by weight
Component: 50~60 parts of white fused alumina, γ-Al2O35~10 parts, 5~10 parts of magnesium aluminate spinel, 0.5~2 part of neodymia, poly- methyl
3~6 parts of methyl acrylate.
Further, above-mentioned proppant internal structure be honeycomb, aperture be 0.5~0.8mm, pore wall thickness be 0.3~
0.8mm。
Further, above-mentioned proppant surface load has catalyst.
The preparation method of above-mentioned proppant includes the following steps:
(1) raw material is weighed according to the proportion；
(2) by γ-Al2O3, magnesium aluminate spinel, neodymia premix uniformly, it is equal to add polymethyl methacrylate mixing
It is even, finally it is uniformly mixed with white fused alumina；
(3) said mixture forms, and green body is made, and spontaneously dries 24~36h；
(4) green body after drying is divided into three phases sintering, and the first stage is 600~900 DEG C of sintering, and second stage is
1000~1200 DEG C of sintering, phase III are 1500~1600 DEG C of sintering.
In above-mentioned steps (4), before sintering, dry base substrate is also needed by the pre-heat treatment, and temperature is 160~200 DEG C, is protected
The warm time is 6~12h.By the pre-heat treatment, keep temperature of charge tentatively uniform, gives full play to the molecular motion in material, favorably
It is uniformly distributed in sintering temperature.
In above-mentioned steps (4), the first stage reaches 4~6h of heat preservation after sintering temperature, after second stage reaches sintering temperature
5~8h is kept the temperature, the phase III reaches 2~4h of heat preservation after sintering temperature.
The sintering process of above-mentioned steps (4) carries out in nitrogen atmosphere.
The advantages of the present invention: the present invention passes through white fused alumina, γ-Al2O3, it is magnesium aluminate spinel, neodymia, poly-
The rational proportion of methyl methacrylate, and by premix, mixing, base, drying, sintering and etc. obtained dense form support
Agent, intensity is high, and impact resistance, acid resistance are good, long service life, are able to extend proppant in coke oven flue gas treatment process
Replacement cycle reduces operating cost.
Specific embodiment
The invention will be further described With reference to embodiment.
There is white fused alumina, γ-Al in composition of raw materials of the present invention2O3, magnesium aluminate spinel, neodymia, poly-methyl methacrylate
Ester is sintered by the first stage, the magnesium aluminate spinel Step crystallization in raw material, ultimately forms complete uniform crystalline state skeleton,
This phase temperature is too low, and crystalline state skeleton is difficult to be formed, and temperature is excessively high, and crystalline state skeleton is easy to collapse, and γ at this time -- Al2O3、
White fused alumina temperature further increases, and molecular motion is very violent, therefore when entering second stage sintering, γ -- Al2O3, Bai Gang
Beautiful amount is far longer than magnesium aluminate spinel, γ -- Al2O3, white fused alumina absorb thermal energy first and start to be sintered, and γ -- Al2O3, it is white
Corundum, which is covered on, can protect the crystalline state skeleton formed on magnesium aluminate spinel, while γ -- Al2O3, white fused alumina and magnalium point
The part of spar contact is capable of forming magnesium-aluminium-oxygen-nitrogen solid solution under nitrogen effect, improves the stability of material microstructure；
When phase III is sintered, above-mentioned magnesium-aluminium-oxygen-nitrogen solid solution is largely formed, and entire material is made to form stable crystalline state skeleton cladding
There is magnesium-aluminium-oxygen-nitrogen solid solution microstructure.And the addition of praseodymium oxide, as crystallization easily in magnesium aluminate spinel sintering process
Core is more easier the formation of crystalline state skeleton, and resulting crystalline state skeleton is also more stable, and polymethyl methacrylate is as bonding
Agent, is cured crosslinking during the sintering process and crystalline state skeleton, magnesium-aluminium-oxygen-nitrogen solid solution cooperate, and further strengthens branch
Support the micro-structural system of agent.Coke oven flue gas itself has containing acids such as sulfide, nitrogen oxides when handling coke oven flue gas
Matter, and flue gas self-temperature is 200~400 DEG C, and proppant is easily corroded at this temperature, to destroy proppant integrality shadow
Treatment effeciency and treatment effect are rung, and proppant of the invention is fine and close by sintering structure, and microstructure is stablized, and is not easy to be rushed
Break up it is bad, be also not easy therefore to can be improved the service life of proppant by the substance corrosion in flue gas.
In addition, proppant obtained can be dropped aperture, hole wall when preparing honeycomb ducts due to intensity height itself
It is low, so that porosity is improved, to avoid fume treatment efficiency is reduced.Proppant surface can supported catalyst, be conducive at raising
Manage efficiency.
Embodiment 1
The present invention provides a kind of desulfurizing and denitrifying process proppant, and raw material includes the component of following parts by weight: Bai Gang
Jade 50 parts, γ-Al2O310 parts, 5 parts of magnesium aluminate spinel, 2 parts of neodymia, 6 parts of polymethyl methacrylate.Inside the proppant
Structure is honeycomb, and the aperture of each honeycomb hole is 0.5~0.8mm, and pore wall thickness is 0.3~0.8mm.
The preparation method of above-mentioned proppant includes the following steps:
(1) raw material is weighed according to the proportion；
(2) by γ-Al2O3, magnesium aluminate spinel, neodymia premix uniformly, it is equal to add polymethyl methacrylate mixing
It is even, finally it is uniformly mixed with white fused alumina；
(3) said mixture forms, and green body is made, and spontaneously dries for 24 hours；
(4) green body after drying is divided into three phases sintering, and carries out in nitrogen atmosphere, and the first stage is 800 DEG C of burnings
Knot, soaking time 6h, second stage are 1200 DEG C of sintering, and soaking time 8h, the phase III is 1500 DEG C of sintering, when heat preservation
Between be 2h.
In above-mentioned steps (4), before sintering, dry base substrate is also needed by the pre-heat treatment, and temperature is 160 DEG C, when heat preservation
Between be 6h.By the pre-heat treatment, keep temperature of charge tentatively uniform, give full play to the molecular motion in material, is conducive to sintering temperature
Degree is uniformly distributed.In addition, the catalyst of proppant surface load can be selected from the oxide of titanium, manganese, vanadium, molybdenum etc., mode of loading
It then can dry, be sintered again by the way that green body to be impregnated in the precursor solution of aforesaid oxides.
Embodiment 2
The present invention provides a kind of desulfurizing and denitrifying process proppant, and raw material includes the component of following parts by weight: Bai Gang
Jade 60 parts, γ-Al2O35 parts, 10 parts of magnesium aluminate spinel, 1 part of neodymia, 5 parts of polymethyl methacrylate.Inside the proppant
Structure is honeycomb, and the aperture of each honeycomb hole is 0.5~0.8mm, and pore wall thickness is 0.3~0.8mm.
The preparation method of above-mentioned proppant includes the following steps:
(1) raw material is weighed according to the proportion；
(2) by γ-Al2O3, magnesium aluminate spinel, neodymia premix uniformly, it is equal to add polymethyl methacrylate mixing
It is even, finally it is uniformly mixed with white fused alumina；
(3) said mixture forms, and green body is made, and spontaneously dries 36h；
(4) green body after drying is divided into three phases sintering, and carries out in nitrogen atmosphere, and the first stage is 600 DEG C of burnings
Knot, soaking time 4h, second stage are 1000 DEG C of sintering, and soaking time 5h, the phase III is 1600 DEG C of sintering, when heat preservation
Between be 4h.
In above-mentioned steps (4), before sintering, dry base substrate is also needed by the pre-heat treatment, and temperature is 200 DEG C, when heat preservation
Between be 8h.By the pre-heat treatment, keep temperature of charge tentatively uniform, give full play to the molecular motion in material, is conducive to sintering temperature
Degree is uniformly distributed.In addition, the catalyst of proppant surface load can be selected from the oxide of titanium, manganese, vanadium, molybdenum etc., mode of loading
It then can dry, be sintered again by the way that green body to be impregnated in the precursor solution of aforesaid oxides.
Embodiment 3
The present invention provides a kind of desulfurizing and denitrifying process proppant, and raw material includes the component of following parts by weight: Bai Gang
Jade 55 parts, γ-Al2O38 parts, 7 parts of magnesium aluminate spinel, 2 parts of neodymia, 3 parts of polymethyl methacrylate.The proppant internal junction
Structure is honeycomb, and the aperture of each honeycomb hole is 0.5~0.8mm, and pore wall thickness is 0.3~0.8mm.
The preparation method of above-mentioned proppant includes the following steps:
(1) raw material is weighed according to the proportion；
(2) by γ-Al2O3, magnesium aluminate spinel, neodymia premix uniformly, it is equal to add polymethyl methacrylate mixing
It is even, finally it is uniformly mixed with white fused alumina；
(3) said mixture forms, and green body is made, and spontaneously dries 30h；
(4) green body after drying is divided into three phases sintering, and carries out in nitrogen atmosphere, and the first stage is 900 DEG C of burnings
Knot, soaking time 5h, second stage are 1100 DEG C of sintering, and soaking time 6h, the phase III is 1600 DEG C of sintering, when heat preservation
Between be 3h.
In above-mentioned steps (4), before sintering, dry base substrate is also needed by the pre-heat treatment, and temperature is 180 DEG C, when heat preservation
Between be 10h.By the pre-heat treatment, keep temperature of charge tentatively uniform, give full play to the molecular motion in material, is conducive to sintering temperature
Degree is uniformly distributed.In addition, the catalyst of proppant surface load can be selected from the oxide of titanium, manganese, vanadium, molybdenum etc., mode of loading
It then can dry, be sintered again by the way that green body to be impregnated in the precursor solution of aforesaid oxides.
Above-mentioned proppant is detected according to SY/T5108-2006, as a result as follows:
Note: acid solubility is to measure after impregnating 48h in 65% hydrochloric acid solution
From upper table result it is found that proppant density height of the invention, compression strength are high, acid resistance is good, is conducive to mention
High service life reduces operating cost.
Proppant of the invention is suitable for dry method, semidry method, wet desulfurizing process, wherein proppant in wet desulfurizing process
The acidic materials touched are more, therefore can preferably embody the acid resistance of proppant of the present invention.It is resulting with embodiment 1
For proppant, in wet desulfurizing process, the proppant of embodiment 1 is layed in absorption tower, is passed through coke oven flue gas from tower bottom,
From tower top injection water to absorb the sulphur-containing substance in coke oven flue gas, the flue gas after absorbing is passed through SCR denitration system removing again
Nitrogen substance.Desulfuration efficiency is 99% or more after tested, and denitration efficiency is 97% or more；And compared with common proppants, make
13% is improved with the service life
The present embodiments relate to the material arrived, reagent and experimental facilities, are to meet industrial waste gas unless otherwise instructed
The commercial product of process field.
The above is merely a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise of not departing from core of the invention technology, improvements and modifications can also be made, these improvements and modifications are also answered
Belong to scope of patent protection of the invention.With any change in the comparable meaning and scope of claims of the present invention, all
It is considered as being included within the scope of the claims.
Claims (7)
1. desulfurizing and denitrifying process proppant, which is characterized in that its raw material includes the component of following parts by weight: white fused alumina 50~
60 parts, γ-Al2O35~10 parts, 5~10 parts of magnesium aluminate spinel, 0.5~2 part of neodymia, 3~6 parts of polymethyl methacrylate.
2. desulfurizing and denitrifying process proppant as described in claim 1, which is characterized in that the proppant internal structure is bee
Nest shape, aperture are 0.5~0.8mm, and pore wall thickness is 0.3~0.8mm.
3. desulfurizing and denitrifying process proppant as described in claim 1, which is characterized in that the proppant surface load is urged
Agent.
4. the preparation method of desulfurizing and denitrifying process proppant as described in claim 1, which is characterized in that including walking as follows
It is rapid:
(1) raw material is weighed according to the proportion；
(2) by γ-Al2O3, magnesium aluminate spinel, neodymia premix uniformly, add polymethyl methacrylate be uniformly mixed, most
It is uniformly mixed with white fused alumina afterwards；
(3) said mixture forms, and green body is made, and spontaneously dries 24~36h；
(4) green body after dry is divided into three phases sintering, and the first stage is 600~900 DEG C of sintering, and second stage is 1000~
1200 DEG C of sintering, phase III are 1500~1600 DEG C of sintering.
5. the preparation method of desulfurizing and denitrifying process proppant as claimed in claim 4, which is characterized in that the step (4)
In, before sintering, dry base substrate is also needed by the pre-heat treatment, and temperature is 160~200 DEG C, and soaking time is 6~12h.
6. the preparation method of desulfurizing and denitrifying process proppant as claimed in claim 4, which is characterized in that the step (4)
In, the first stage reaches 4~6h of heat preservation after sintering temperature, and second stage keeps the temperature 5~8h after reaching sintering temperature, and the phase III reaches
2~4h is kept the temperature after to sintering temperature.
7. the preparation method of desulfurizing and denitrifying process proppant as claimed in claim 4, which is characterized in that the step (4)
Sintering process carried out in nitrogen atmosphere.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110606728A (en) * | 2019-09-21 | 2019-12-24 | 河南祥盛陶粒有限公司 | Light microporous ceramsite sand and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110606728A (en) * | 2019-09-21 | 2019-12-24 | 河南祥盛陶粒有限公司 | Light microporous ceramsite sand and preparation process thereof |
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