CN104130818A - Oil shale semi-coke activator, and preparation method and application thereof - Google Patents
Oil shale semi-coke activator, and preparation method and application thereof Download PDFInfo
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- CN104130818A CN104130818A CN201310723470.6A CN201310723470A CN104130818A CN 104130818 A CN104130818 A CN 104130818A CN 201310723470 A CN201310723470 A CN 201310723470A CN 104130818 A CN104130818 A CN 104130818A
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Abstract
The invention provides an oil shale semi-coke activator. The oil shale semi-coke activator is prepared from an oil shale semi-coke composite main body, barium nitrate powder and iron powder. The oil shale semi-coke composite main body is prepared by doping Ce into a zirconia powder functional material with a micro-nano structure, wherein the zirconia powder functional material is composed of innumerous particles with particle sizes in a range of 5 to 10 mu m, micropores with sizes in a range of 50 to 100 nm are distributed on the surface of the zirconia powder functional material, a ratio of the functional material to Y(NO3)3.5H2O to Zr(NO3)4.5H2O is 1: 1: 1, and a mol ratio of zirconium to cerium in a carrier is 99: 1. The oil shale semi-coke composite main body, barium nitrate powder and iron powder sum to 100%, and a ratio of the oil shale semi-coke composite main body to barium nitrate powder to iron powder is 30-80%: 5-35%: 5-35%. The oil shale semi-coke activator, yellow mud and oil shale semi-coke powder are mixed according to a ratio of 1: 1: 98, then a wetting amount of water is added, and uniform mixing with stirring and molding are carried out to obtain an oil shale semi-coke mixture; and the oil shale semi-coke mixture generates heat of more than 3000 Kcal/Kg during combustion and has Ringelman emittance of almost grade 0.
Description
Technical field
The invention belongs to type material, comprehensive utilization of resources, novel energy, field of environment protection, provides a kind of oil shale semi-coke activator and preparation method and application.
Background technology
Resinous shale (oil shale) claims that again oil shale is a kind of sedimentogeneous rock that is rich in organic matter (approximately 5% one 50%).Resinous shale belongs to the sapropelinite class of high mineral, is low heat value solid fossil fuel, and its look light gray is to deeply brown.Resinous shale contains two kinds of organic matters: a kind of is pitch, and relative content seldom, dissolves in organic solvent; Another kind of for being insoluble to the high molecular polymer of organic solvent, claim kerogen (kerogen).Resinous shale is a kind of important energy, and in fossil oil, its storage capacity is converted to thermal value and is only second to coal and row second.
Oil shale semi-coke (hereinafter referred to as " semicoke ") refers to that resinous shale heats the in the situation that of completely cutting off air in gas retort, makes organic matter degradation produce the solid-state waste residue being left after shale oil, carbonizing gas.As the waste residue after oil refining, semicoke has 3600～4000kJ/kg calorific value, accounts for 40～50% of resinous shale gross calorific value.Its volatile content is low, and ash content is very large, and calorific value is very low, is a kind of inferior fuel that is difficult to catch fire, be difficult to after-flame; And exploitation resinous shale out, wherein the following chip of 8mm accounts for 1/4 left and right and can not, for oil refining, can only directly send into power station.
Oil Shale Resource in Jilin Province proven reserve is 176.76 hundred million t, accounts for 56% of national reserves, is converted to shale oil and is 1.4 times of our province primary energy source (coal+oil+Sweet natural gas+waterpower) total resources.In resinous shale, shale oil accounts for greatly shale total calorific value 50% left and right, if refined oil merely, can only utilize at most half of shale heat, causes significant wastage.The semicoke obtaining after oil shale distillation contains organic composition and fixed carbon, has certain calorific value, but mainly as waste heap, abandons at present, takies a large amount of arable lands.In semicoke, also contain lot of trace metallic element, half volatile material polynuclear aromatics, oil, phenolic compound, sulfide and other material, if do not administered, will cause severe contamination to environment.
The oil shale reserves of our province Huadian City is 1,000,000,000 tons, and wherein, workable reserves is about 400,000,000 tons.This regional resinous shale oil length, up to 10% to 20%, is the highest high-quality, the higher-grade resinous shale of oil length in current domestic explored oil shale resources.In Huadian, built up at present and produced few hundred thousand tonnes of shale oil destructive distillation factory per year, produced every year 200000-500,000 tons of oil shale semi-cokes.Because semicoke is difficult to burning, can not directly make building block again, there is technical bottleneck for generating in semicoke, so these solid waste need effective technology to be changed into available resource.
In order to solve resinous shale problem of complex utilization, promote the development of oil shale industry, by analysing in depth the physicochemical characteristic of resinous shale and the problem that existing destructive distillation oil refining factory, power station exist, resinous shale comprehensive utilization integrated technology has been proposed.This technology is utilized the mixed firing generating in boiler of the discarded chip resinous shale of destructive distillation oil refining factory, semicoke (slag) and tail gas, and the lime-ash of boiler has low, the active good feature of carbon content, can all send into Building Materials Factory and manufacture the building materials such as cement, building block, haydite.Like this, oil shale mine, destructive distillation oil refining factory, circular fluid bed power station and Building Materials Factory form Yi Ge chain-belt type associated enterprises jointly, making resinous shale is shale oil and electric power as energy conversion, as resource conversion, be building materials again, realization is without the comprehensive utilization of solid waste discharge, formed like this resinous shale comprehensive utilization integrated technology and Mode of Circular, its economic benefit is more much higher than the single utilization of resinous shale, and environmental and social benefits is better.Yet the most of resinous shale in present Jilin Province are developed the problem facing and are, most input concentrates on the best destructive distillation oil refining part of benefit, a large amount of the piling up of semicoke of generation, and producer is not high to the enthusiasm of its processing.From technological layer, oil shale semi-coke contains certain combustiblematerials, after must burning, just can make building block, but the calorific value of burning is very low, produces larger flue dust, usually from horizontal blanking.Mixed firing is a kind of solution, but input-output are lower, and ash content is large, and investment is not calculated very much.Therefore, need better technology that oil shale semi-coke is converted into the fuel of the market competitiveness to produce good economic benefit.
Summary of the invention
The object of the invention is to solve problems of the prior art, provide a kind of and can activate inert fraction in oil shale semi-coke, realize the abundant burning of oil shale semi-coke.
Technical scheme of the present invention is: a kind of oil shale semi-coke activator is to be made by the compound host of oil shale semi-coke, nitrate of baryta powder and iron powder; The compound host of described oil shale semi-coke is that the Zirconium oxide powder functional materials that has a micro-nano structure by Ce doping is carrier, adheres to Y(NO
3)
35H
2o and Zr(NO
3)
45H
2two kinds of reagent of O form, and in carrier, the mol ratio of zirconium and cerium is 99:1; Described Zirconium oxide powder functional materials is the particle by countless 5～10 μ m, and the distributing micropore of 50～100nm of particle surface wherein forms Ce doped zirconia powder functional materials and the Y(NO of the compound host carrier of oil shale semi-coke
3)
35H
2o and Zr(NO
3)
45H
2the mass ratio 1:1:1 of O; The mass ratio of the compound host of described oil shale semi-coke and nitrate of baryta powder and iron powder is (30%～80%): (5%～35%): (5%～35%), the quality sum of the compound host of oil shale semi-coke and nitrate of baryta powder and iron powder is 100%.
The preparation method of above-mentioned a kind of oil shale semi-coke activator, gets Y(NO
3)
35H
2o and Zr(NO
3)
45H
2o is soluble in water, obtains active ingredient Y
3+, Zr
4+solution, then add the Ce doping ZrO with micro-nano structure
2powder functional materials carrier, ultrasonic dispersion, makes Y
3+, Zr
4+active constituent loading is in the ZrO with micro-nano structure
2on powder functional materials carrier; Then the moisture in evaporate to dryness solution under 90 ℃ of conditions, makes the compound host of oil shale semi-coke, wherein, and water and Y(NO
3)
35H
2o, Zr
2(NO
3)
45H
2o and the Ce doping ZrO with micro-nano structure
2the mass ratio of powder functional materials is: 50:1:1:1; In the compound host of oil shale semi-coke, add nitrate of baryta powder and iron powder again, making their sums is 100%, wherein, the mass ratio of the compound host of oil shale semi-coke and nitrate of baryta powder and iron powder is (30%～80%): (10%～35%): (10%～35%), mixes and obtain oil shale semi-coke activator.
A kind of Ce doping ZrO with micro-nano structure
2powder functional materials, it is to be made by following presoma: zirconium oxychloride, cerous nitrate, hexamethylenetetramine, polystyrene polymer template, ethanol; Wherein, the mol ratio of zirconium oxychloride and hexamethylenetetramine is 1:3; The mol ratio of zirconium oxychloride and cerous nitrate is 99:1; Zirconium oxychloride is 1:1～1:2 with described polystyrene polymer template quality ratio; The consumption of ethanol is that every gram of zirconium oxychloride adds 10ml; Its preparation method is as follows: after described zirconium oxychloride, cerous nitrate are reacted in water with hexamethylenetetramine, heated constant temperature 20 minutes, obtains Zr(OH)
4the translucent colloidal sol of presoma, polystyrene polymer template is added in above-mentioned colloidal sol and stirred, after centrifugal oven dry, in ethanolic soln, soak, dry again and burn 1h in 1000 ℃ of following temperature, obtain the particle of countless 5～10 μ m, the distributing surface of 50～100nm micropore of particle surface has the Ce doping ZrO of micro-nano structure
2powder functional materials.
A kind of Ce doping ZrO with micro-nano structure of the above
2the preparation method of powder functional materials, it is to be made by following presoma: zirconium oxychloride, cerous nitrate, hexamethylenetetramine, polystyrene polymer template, ethanol; Wherein, the mol ratio of zirconium oxychloride and hexamethylenetetramine is 1:3; The mol ratio of zirconium oxychloride and cerous nitrate is 99:1; Zirconium oxychloride is 1:1～1:2 with described polystyrene polymer template quality ratio; The consumption of ethanol is that every gram of zirconium oxychloride adds 10ml; Its preparation method is as follows: after described zirconium oxychloride is reacted in water with hexamethylenetetramine, be heated to 95 ℃ of constant temperature 20 minutes, obtain Zr(OH)
4presoma vitreosol, polystyrene polymer template is added in above-mentioned colloidal sol and stirs 1h, after centrifugal, after 85 ℃ of oven dry 1h, in the ethanolic soln of 10ml 97wt%, soak 10min, dry 6h for 85 ℃ again, and burn 1h in 1000 ℃ of following temperature, obtain the particle of countless 5～10 μ m, the distributing surface of 50～100nm micropore of particle surface has the ZrO of micro-nano structure
2powder functional materials.
The application of a kind of oil shale semi-coke activator of the above, by the oil shale semi-coke powder under oil shale semi-coke activator and yellow mud, 40～80 mesh sieves, after mixing according to the ratio of mass ratio 1:1:98, add the water of wetting quantity to stir well, with the oil shale semi-coke mixture after molding coal machine sizing, the heat > 3000Kcal/Kg that burning produces, and without any flue gas, produce in combustion processes, lingemann blackness is close to 0 grade.
Substantive distinguishing features and a marked improvement are compared with prior art had in the present invention.
It is carrier that the Ce doping ZrO2 powder functional materials with micro-nano structure is take in the present invention, its area load Y
3+, Zr
4+active ingredient, makes its surface increase multiple combustion-supporting composition, prepares the activator of catalyticcombustion oil shale semi-coke.Experiment shows, after this activator fully mixes with oil shale semi-coke powder, can promote combustiblecomponents fully to react with combustion-supporting composition.React generation new compound and emit heat with aluminium and element silicon in oil shale semi-coke simultaneously, further promoting burning.
Contriver once applied for patent of invention " activating coal gangue agent and preparation method and application " last year, and patent of invention number is: 201210323934.X.This patent has been described the preparation and application of activating coal gangue agent.By contrast verification, contriver finds that activating coal gangue agent can not fully be applicable to the burn application of oil shale semi-coke, and major cause is in oil shale semi-coke, to contain a certain proportion of heavy oil composition, needs more suitable catalyzer to come fully to its catalysis.Activator of the present invention is through adjusting and improving, to obtain on the basis of activating coal gangue agent, is more applicable for composition and the character of Huadian Oil Shale semicoke.Oil shale semi-coke activator of the present invention is by mixing with the ratio row of 1%:1%:98% mass percent with oil shale semi-coke, tackiness agent loess, can greatly promote the burning of oil shale semi-coke, more than thermal value reaches 3500Kcal/Kg, in combustion processes, without any flue gas, produce, lingemann blackness is close to 0 grade.
That the present invention uses is wetting ability ZrO
2, the bake out temperature of choosing and drying time are best, only, under preferred ethanol consumption, bake out temperature and time conditions, the productive rate of product is the highest, and the wetting ability of material is also best.
Embodiment
Below by embodiment, the invention will be further described.
The ZrO 1, with micro-nano structure
2the preparation method of powder functional materials.
The Ce doping ZrO with micro-nano structure
2powder functional materials is to be made by following presoma: zirconium oxychloride, cerous nitrate, hexamethylenetetramine, polystyrene polymer template, ethanol; Wherein, the mol ratio of zirconium oxychloride and hexamethylenetetramine is 1:3; The mol ratio of zirconium oxychloride and cerous nitrate is 99:1; Zirconium oxychloride is 1:1～1:2 with described polystyrene polymer template quality ratio; Every gram of zirconium oxychloride adds the ethanolic soln 10ml of 97wt%; Drying dehydration and high-temperature roasting make described ZrO
2powder functional materials; Its preparation method is as follows: after described zirconium oxychloride, cerous nitrate are reacted in water with hexamethylenetetramine, be heated to 95 ℃ of constant temperature 20 minutes, obtain Zr(OH)
4presoma vitreosol, polystyrene polymer template is added in above-mentioned colloidal sol and stirs 1h, after centrifugal, after 85 ℃ of oven dry 1h, in the ethanolic soln of 10ml 97wt%, soak 10min, dry 6h for 85 ℃ again, and burn 1h in 1000 ℃ of following temperature, obtain the particle of countless 5～10 μ m, the distributing surface of 50～100nm micropore of particle surface has the ZrO of micro-nano structure
2powder functional materials.
The ethanolic soln 10ml that adds 97wt% in every gram of zirconium oxychloride of the present invention, ethanol consumption is few, disperses bad; Many concentrated power consumptions, used time are high; That use is wetting ability ZrO
2, the bake out temperature of choosing and drying time are best, only, at above-mentioned preferred ethanol consumption, only, under such temperature and time condition, the productive rate of product is the highest, and the wetting ability of material is also best.
2
,the composition of oil shale semi-coke activator.
A kind of oil shale semi-coke activator is to be made by the compound host of oil shale semi-coke, nitrate of baryta powder and iron powder; The compound host of described oil shale semi-coke is the particle by countless 5～10 μ m, the distributing Ce doping ZrO with micro-nano structure of 50～100nm micropore of particle surface
2powder functional materials is carrier, adheres to Y(NO
3)
35H
2o and Zr(NO
3)
45H
2o forms; Wherein form the Ce doping ZrO of the compound host of oil shale semi-coke
2powder functional materials and Y(NO
3)
35H
2o and Zr(NO
3)
45H
2the mass ratio 1:1:1 of O; The mass ratio of the compound host of described oil shale semi-coke and nitrate of baryta powder and iron powder is (30%～80%): (10%～35%): (10%～35%).
3, the preparation of oil shale semi-coke activator.
The preparation method of above-mentioned a kind of oil shale semi-coke activator, gets Y(NO
3)
35H
2o and Zr(NO
3)
45H
2o is soluble in water, obtains active ingredient Y
3+, Zr
4+solution, then add to have the Ce doping ZrO of micro-nano structure
2powder functional materials is carrier, and ultrasonic dispersion, makes Y
3+, Zr
3+active constituent loading is in the Ce doping ZrO with micro-nano structure
2on powder functional materials carrier; Then the moisture in evaporate to dryness solution under 90 ℃ of conditions, makes the compound host of oil shale semi-coke.Wherein, water and Y(NO
3)
35H
2o, Zr(NO
3)
45H
2o and the Ce doping ZrO with micro-nano structure
2the mass ratio of powder functional materials is: 50:1:1:1; In the compound host of oil shale semi-coke, add nitrate of baryta powder and iron powder again, making their sums is 100%, wherein, the mass ratio of the compound host of oil shale semi-coke and nitrate of baryta powder and iron powder is (30%～80%): (10%～35%): (10%～35%), mixes and obtain oil shale semi-coke activator.
4, the application of oil shale semi-coke activator.
The application of oil shale semi-coke activator as previously discussed, by yellow mud with after oil shale semi-coke powder under 40～80 mesh sieves mixes according to the ratio of mass ratio 1:1:98, add the water of wetting quantity to stir well, with the type of the making oil shale semi-coke fuel mixture after molding coal machine sizing, the heat that burning produces is 2500 ~ 3500cal/Kg, and in combustion processes, without any flue gas, produce, lingemann blackness is close to 0 grade.
embodiment 1
Get 0.537g zirconium oxychloride and be dissolved in 15ml water, after adding about 0.004g cerous nitrate and 0.72g hexamethylenetetramine to dissolve, on heating jacket, heat.The power of heating jacket is 800W.When solution temperature reaches 95 ℃, keep 30min, obtain Zr (OH)
4presoma clear solution, immerses soaking and stirring 1h in described colloidal sol by the polystyrene polymer template of 1.111g.In 85 ℃ of baking ovens, dry 1 h to remove moisture wherein after centrifugal, then at the alcohol solution dipping 10min of 10ml 97wt%, then dry 6 h in 85 ℃, then at 1000 ℃, burn 1h, obtain ZrO2 functional materials.Get 0.2gY(NO
3)
35H
2o and 0.2gZr(NO
3)
45H
2o is dissolved in 10ml water, adds above-mentioned ZrO
2the ultrasonic dispersion of powder 0.2g.Under 90 ℃ of conditions, moisture in evaporate to dryness solution, obtains activating host.In activator host, add 0.2g iron powder and 0.2g nitrate of baryta powder, mix and obtain oil shale semi-coke activator.
Getting activator powder 1g mixes with 1g loess (clay) powder, join pulverize after under 40～80 mesh sieves in oil shale semi-coke powder 98g, make oil shale semi-coke fuel mixture, then mix, add again 10ml water, after stirring, with molding coal machine, be extruded to shape, make type oil shale semi-coke combustible mixture.
embodiment 2
Get 0.537g zirconium oxychloride and be dissolved in 15ml water, after adding about 0.004g cerous nitrate and 0.72g hexamethylenetetramine to dissolve, on heating jacket, heat.The power of heating jacket is 800W.When solution temperature reaches 95 ℃, keep 30min, obtain Zr (OH)
4presoma clear solution, immerses soaking and stirring 1h in described colloidal sol by the polystyrene polymer template of 1.111g.After centrifugal, in 85 ℃ of baking ovens, dry 1 h to remove moisture wherein, then in the ethanolic soln of 10ml 97wt%, soak 10min, then in 85 ℃ of oven dry 6 h, then at 900 ℃, burn 1h, obtain ZrO
2functional materials.Get 0.2gY(NO
3)
35H
2o and 0.2gZr(NO
3)
45H
2o is dissolved in 10ml water, adds the above-mentioned ultrasonic dispersion of Zirconium oxide powder 0.2g.Under 90 ℃ of conditions, moisture in evaporate to dryness solution, obtains activating host.In activator host, add 0.04g iron powder and 0.04g nitrate of baryta powder, mix and obtain oil shale semi-coke activator.
Getting activator powder 1g mixes with 1g loess stick powder, join pulverize after under 40～80 mesh sieves in oil shale semi-coke powder 98g, make oil shale semi-coke fuel mixture, then mix, add again 10ml water, after stirring, with molding coal machine, be extruded to shape, make type oil shale semi-coke combustible mixture.
embodiment 3
Get 0.537g zirconium oxychloride and be dissolved in 15ml water, after adding about 0.004g cerous nitrate and 0.72g hexamethylenetetramine to dissolve, on heating jacket, heat.The power of heating jacket is 800W.When solution temperature reaches 95 ℃, keep 30min, obtain Zr(OH)
4presoma clear solution, immerses soaking and stirring 1h in described colloidal sol by the polystyrene polymer template of 1.111g.After centrifugal, in 85 ℃ of baking ovens, dry 1 h to remove moisture wherein, then in the ethanolic soln of 10ml 97wt%, soak 10min, then in 85 ℃ of oven dry 6 h, then at 900 ℃, burn 1h, obtain ZrO2 functional materials.Get 0.2gY(NO
3)
35H
2o and 0.2gZr(NO
3)
45H
2o is dissolved in 10ml water, adds the above-mentioned ultrasonic dispersion of Zirconium oxide powder 0.2g.Under 90 ℃ of conditions, moisture in evaporate to dryness solution, obtains activating host.In activator host, add 0.1g iron powder and 0.1g nitrate of baryta powder, mix and obtain oil shale semi-coke activator.
Getting activator powder 1g mixes with 1g loess binder powders, join pulverize after under 40～80 mesh sieves in oil shale semi-coke powder 98g, make oil shale semi-coke fuel mixture, then mix, add again 10ml water, after stirring, with molding coal machine, be extruded to shape, make type oil shale semi-coke combustible mixture.
embodiment 4(the mensuration of dry oil shale semi-coke heat output of fuel
)
In combustion boat, take the dry oil shale semi-coke fuel sample 1.1g that granularity is less than 0.2 ㎜, then combustion boat is packed in the dry cooker racks of oxygen bomb.Get one section of ignition wire (diameter 0.12mm, length 90mm, 50 joules of calorific values, two ends are connected on respectively on two electrode columns of oxygen bomb, crooked ignition wire approaches sample.In oxygen bomb, add 10ml distilled water, tighten oxygen bomb lid.Automatically oxygen spring heat meter adopts the instrument (model: FX-DM3200) that Beijing produces with moral foundation Science and Technology Ltd..Starting instrument and carry out calorimetric measurement, is 3305cal/Kg through testing and calculate the thermal value of sample.
embodiment 5(the measurement of the fuel gas blackness of oil shale semi-coke forming mixture
)
The combustion experiment of sample is the same with traditional combustion processes.Take oil shale semi-coke shaped fuel 20kg and put into handwarmer, the charcoal of getting burning drops into and ignites.Handwarmer flue opening is in outdoor eminence.Burning starts rear with its blackness of CN60M/HC10 lingemann blackness instrumentation amount.Observation process occurs in sunny daytime, and observation angle and sunlight are 90 degree.With lingemann blackness meter left side eyepiece, by Smoke target and the comparison of this grade of gray scale ladder block, every 5 minutes records once, get observation mean value ten times, finally record blackness between 0 grade and 1 grade.
Claims (5)
1. an oil shale semi-coke activator, is to be made by the compound host of oil shale semi-coke, nitrate of baryta powder and iron powder; The compound host of described oil shale semi-coke is that the Zirconium oxide powder functional materials that has a micro-nano structure by Ce doping is carrier, adheres to Y(NO
3)
35H
2o and Zr(NO
3)
45H
2two kinds of reagent of O form, and in carrier, the mol ratio of zirconium and cerium is 99:1; Described Zirconium oxide powder functional materials is the particle by countless 5～10 μ m, and the distributing micropore of 50～100nm of particle surface wherein forms Ce doped zirconia powder functional materials and the Y(NO of the compound host carrier of oil shale semi-coke
3)
35H
2o and Zr(NO
3)
45H
2the mass ratio 1:1:1 of O; The mass ratio of the compound host of described oil shale semi-coke and nitrate of baryta powder and iron powder is (30%～80%): (5%～35%): (5%～35%), the quality sum of the compound host of oil shale semi-coke and nitrate of baryta powder and iron powder is 100%.
2. the preparation method of a kind of oil shale semi-coke activator as claimed in claim 1, gets Y(NO
3)
35H
2o and Zr(NO
3)
45H
2o is soluble in water, obtains active ingredient Y
3+, Zr
4+solution, then add the Ce doping ZrO with micro-nano structure
2powder functional materials carrier, ultrasonic dispersion, makes Y
3+, Zr
4+active constituent loading is in the ZrO with micro-nano structure
2on powder functional materials carrier; Then the moisture in evaporate to dryness solution under 90 ℃ of conditions, makes the compound host of oil shale semi-coke, wherein, and water and Y(NO
3)
35H
2o, Zr
2(NO
3)
45H
2o and the Ce doping ZrO with micro-nano structure
2the mass ratio of powder functional materials is: 50:1:1:1; In the compound host of oil shale semi-coke, add nitrate of baryta powder and iron powder again, making their sums is 100%, wherein, the mass ratio of the compound host of oil shale semi-coke and nitrate of baryta powder and iron powder is (30%～80%): (10%～35%): (10%～35%), mixes and obtain oil shale semi-coke activator.
3. a Ce doping ZrO with micro-nano structure
2powder functional materials, it is to be made by following presoma: zirconium oxychloride, cerous nitrate, hexamethylenetetramine, polystyrene polymer template, ethanol; Wherein, the mol ratio of zirconium oxychloride and hexamethylenetetramine is 1:3; The mol ratio of zirconium oxychloride and cerous nitrate is 99:1; Zirconium oxychloride is 1:1～1:2 with described polystyrene polymer template quality ratio; The consumption of ethanol is that every gram of zirconium oxychloride adds 10ml; Its preparation method is as follows: after described zirconium oxychloride, cerous nitrate are reacted in water with hexamethylenetetramine, heated constant temperature 20 minutes, obtains Zr(OH)
4the translucent colloidal sol of presoma, polystyrene polymer template is added in above-mentioned colloidal sol and stirred, after centrifugal oven dry, in ethanolic soln, soak, dry again and burn 1h in 1000 ℃ of following temperature, obtain the particle of countless 5～10 μ m, the distributing surface of 50～100nm micropore of particle surface has the Ce doping ZrO of micro-nano structure
2powder functional materials.
4. a kind of Ce doping ZrO with micro-nano structure as claimed in claim 3
2the preparation method of powder functional materials, it is to be made by following presoma: zirconium oxychloride, cerous nitrate, hexamethylenetetramine, polystyrene polymer template, ethanol; Wherein, the mol ratio of zirconium oxychloride and hexamethylenetetramine is 1:3; The mol ratio of zirconium oxychloride and cerous nitrate is 99:1; Zirconium oxychloride is 1:1～1:2 with described polystyrene polymer template quality ratio; The consumption of ethanol is that every gram of zirconium oxychloride adds 10ml; Its preparation method is as follows: after described zirconium oxychloride is reacted in water with hexamethylenetetramine, be heated to 95 ℃ of constant temperature 20 minutes, obtain Zr(OH)
4presoma vitreosol, polystyrene polymer template is added in above-mentioned colloidal sol and stirs 1h, after centrifugal, after 85 ℃ of oven dry 1h, in the ethanolic soln of 10ml 97wt%, soak 10min, dry 6h for 85 ℃ again, and burn 1h in 1000 ℃ of following temperature, obtain the particle of countless 5～10 μ m, the distributing surface of 50～100nm micropore of particle surface has the ZrO of micro-nano structure
2powder functional materials.
5. the application of a kind of oil shale semi-coke activator as claimed in claim 1, by the oil shale semi-coke powder under oil shale semi-coke activator and yellow mud, 40～80 mesh sieves, after mixing according to the ratio of mass ratio 1:1:98, add the water of wetting quantity to stir well, with the oil shale semi-coke mixture after molding coal machine sizing, the heat > 3000Kcal/Kg that burning produces, and without any flue gas, produce in combustion processes, lingemann blackness is close to 0 grade.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310723470.6A CN104130818A (en) | 2013-12-25 | 2013-12-25 | Oil shale semi-coke activator, and preparation method and application thereof |
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| CN112695587A (en) * | 2020-12-17 | 2021-04-23 | 深圳市夺天工环境建设有限公司 | Urban and rural garden antiskid type brick that permeates water |
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