CN103801387A - Carbocoal-based photo-catalytic oxidation fuel gas desulfurization and denitration agent and preparation method thereof - Google Patents

Carbocoal-based photo-catalytic oxidation fuel gas desulfurization and denitration agent and preparation method thereof Download PDF

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CN103801387A
CN103801387A CN201210457971.XA CN201210457971A CN103801387A CN 103801387 A CN103801387 A CN 103801387A CN 201210457971 A CN201210457971 A CN 201210457971A CN 103801387 A CN103801387 A CN 103801387A
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semicoke
catalytic oxidation
desulphurization
carbocoal
agent
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李春虎
孙圣楠
郑昱
王群
冯丽娟
卞俊杰
王亮
李子真
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Ocean University of China
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Ocean University of China
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • YGENERAL 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
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Abstract

The invention discloses a carbocoal-based photo-catalytic oxidation fuel gas desulfurization and denitration agent and a preparation method thereof. The preparation method is characterized in that carbon-containing materials such as lignite carbocoal, anthracitic coal and bituminous coal carbocoal take amorphous or formed particle carbocoal, tetrabutyl titanate, absolute ethyl alcohol and the like as photo-catalyst active raw materials; firstly, the amorphous or formed particle carbocoal supports a photo-catalyst TiO2, transition metal oxide and the like through methods of ultrasonic activation of hydrogen peroxide, acid activation, alkaline activation and the like, and subsequently, the amorphous or formed particle carbocoal is activated by water vapour at a high temperature of 500-700 DEG C and then mechanically mixed with ZSM-5 or other NO adsorption molecular sieves, thereby finally obtaining the photo-catalytic desulfurization and denitration agent. The carbocoal-based photo-catalytic oxidation fuel gas desulfurization and denitration agent has the characteristics of extensive sources and low price of active carbocoal; after TiO2 is supported, the carbocoal-based photo-catalytic oxidation fuel gas desulfurization and denitration agent has the effect of getting twice the result with half the effort during denitration; the ZSM-5 and other NO absorption molecule sieves can play the role of capturing NO; the prepared catalyst can be used for removing NOx in fuel gas of coal-fired power plants, coal-fired boilers, coal-fired kilns and the like through a low-temperature photo-catalytic oxidation method at a temperature which is less than or equal to 110 DEG C; the prepared catalyst also can be used for removing NOx in ventilated gases generated in road tunnels, underground parking garages, street intersections and the like.

Description

A kind of for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent and preparation method thereof
Technical field
The present invention relates to one can utilize photocatalytic oxidation to remove NO in flue gas xadsorption catalyst and technology of preparing thereof, more specifically say that one can metal oxide-loaded and TiO 2, and with the technology of preparing of the active carbocoal base optic catalytic oxidation and denitration adsorption catalyst of molecular sieve mechanical mixture.
Background technology
NO in the coal-fired flue-gas of the whole nation xone of major pollutants of atmospheric environment.From the detection case year by year of China, since the nineties in last century, concentration and the settling amount of nitrate in rainfall just progressively rises, and in precipitation, the ratio of nitrate and sulfate changes, and the acid rain of China is just towards H 2sO 4with HNO 3mixed type acid rain changes.In Beijing, the ground such as Guangzhou, Pearl River Delta, Hong Kong, NO xconcentration exceeded SO 2.According to State Statistics Bureau's statistics, 2007 annual China coal-fired flue-gas NO xdischarge capacity is about 1797.70 ten thousand tons, wherein NO in industrial waste gas xdischarge capacity is 1223.97 ten thousand tons.If do not strengthened NO xcontrol, NO from now on xthe major pollutants of In The Atmosphere Over China pollution will be become.
NO xbe generally acknowledged environment harmful gas, the harm of environmental and human health impacts is mainly contained to following several respects: the first, NO xthe major pollutants that form acid rain, acid mist; The second, NO xto the intoxicating effect of human body.That wherein harm is maximum is NO 2, major effect respiratory system, can cause the disease such as bronchitis and pulmonary emphysema; The 3rd, NO xto the infringement of plant; The 4th, NO xcan form photochemical fog with hydrocarbon; The 5th, NO xparticipate in the destruction of ozone layer.
With NH 3for NO is reduced to N by reducing agent 2sCR (SCR) technology and SNCR (SNCR) technology be NO in current removal flue gas xthe most frequently used method.There is following shortcoming in the method: (1) catalyst is expensive TiO 2base, unreasonable economically; (2) must strictly control NH 3with the stoichiometric proportion of NO, otherwise unreacted NH 3to cause secondary pollution, in addition NH 3the equipment corrosion problem that leakage causes is difficult to avoid and overcome; (3) SCR reaction temperature generally must be more than 200 ℃, and NSCR technology need, more than 700 ℃, be mated with electric cleaner temperature is bad, causes dust more serious to the wearing and tearing of catalyst, and energy consumption is higher; (4) SO 2to de-NO xthere is facilitation, de-NO xneed be arranged on before desulfurization, cause the perishable and dust etching of equipment; (5) operating condition harshness, source of the gas needs pretreatment to prevent catalyst poisoning.
On the other hand.Locate the NO in ventilating opening from tunnel, underground parking and crossing, street etc. xconcentration extremely low, generally lower than 10ppm, and temperature is generally normal temperature.In this case, if utilize SCR or SNCR technology, need ℃ even higher air heat to 200, this just needs a large amount of heat energy and special heating and heat-exchange apparatus investment.
Low temperature photocatalytic oxidation denitration technology refers under the effect of photochemical catalyst, and NO can or be NO a little more than the lower catalytic oxidation of condition (≤130 ℃) of normal temperature at normal temperature 2, then use absorbent (as NaOH, Na 2cO 3with ammoniacal liquor etc.) or adsorbent (active carbon and active carbocoal material or molecular sieve etc.) by NO 2absorb, according to the difference of reproducing adsorbent and absorbent, catalytic oxidation product NO 2can be converted into rare nitric acid, ammonium nitrate, ammonium nilrite etc.In addition, this active carbocoal base desulphurization and denitration agent also has certain SO concurrently 2remove ability.
Photocatalysis has immeasurable prospect, TiO in denitration field 2as the material with good photocatalysis performance, be applied to photocatalysis denitration technology.And the active carbon (Jiao) with absorption property is TiO 2good carrier.By TiO 2load on active carbocoal, add transition metal ions to TiO 2carry out modification, to widen TiO 2spectral absorption scope, meanwhile, transition metal ions can carry out modification to semicoke, strengthens the ability of its catalytic oxidation denitration, therefore plays a multiplier effect.Molecular sieve has the ability of high selectivity absorption NO, and molecular sieve is mixed with photochemical catalyst again, more can play the effect of multiplication agent, significantly improves its denitration activity.
The photocatalysis oxidation method byproduct producing of regenerating: nitrate, or ammonium salt (ammonium sulfate, ammonium nitrate, ammonium nilrite), can be used as fertilizer and sell and produce economic benefit, realize the maximization added value of N recycling.
At present, mainly contain molecular sieve, active carbon, various loaded noble metal catalyst and catalyst of transition metal oxide etc. for the catalyst of catalytic oxidation NO.Wherein, active carbon, with its special pore structure, large specific area and abundant surface functional group, becomes a kind of good solid absorption catalyst.And the low temperature photochemical catalytic oxidation relating at this patent removes NO xin technology, it can make the catalytic oxidant of NO equally, also can be used as catalysate NO 2adsorbent.At low temperatures, activated-carbon catalyst catalytic oxidation NO is NO 2activity very high.The greatest problem of activated-carbon catalyst catalytic oxidation NO is that catalytic activity reduces rapidly with the rising of temperature at present; In flue gas, the existence of water vapour makes the conversion ratio of activated carbon catalysis oxidation NO be difficult to improve; NO is very weak in the chemisorbed on active carbon (Jiao) surface, and its activated adoption position is easily replaced by steam, and NO does not bring into play the absorption activation of ultraviolet light and visible ray simultaneously; Active carbon involves great expense, and has limited promoting the use of of absorbent charcoal based catalyst.
Semicoke is that weak caking coal low temperature (500~800 ℃) destructive distillation (refers to that coal is under isolated air conditions, decomposes generates semicoke, coalite tar, coal gas and pyrolysis water process) the flammable solid product of gained, look black porous, main component is carbon, ash content and volatile matter.Because not yet pyrolysis is complete, more hydrogen and oxygen are contained in inside, more rich hole and surface texture.Most scholar's research show, raw coal character and the process conditions of preparing semicoke have a great impact its performance.Different from conventional active carbon, active carbocoal is a kind of comprehensive strength (withstand voltage, wear-resistant, shock-resistant) carbon adsorbing material that specific activity charcoal is high, specific area specific activity charcoal is little.Domesticly disclosedly adopt SCR method about the catalyst in denitration patent, the desulphurization and denitration agent that can be used for low-temperature catalytic oxidation technology is less more.Wherein (publication number CN1919447A) is houghite material.And the middle publication of semicoke as catalyst or adsorbent of using is applied to gas sweetening (SO more 2and H 2s) be or Desulphurization of fuels, extrusion molding semicoke for the semicoke of the patent 1 (publication number CN101362101A) of denitration.
Summary of the invention
The deficiency existing for prior art, a kind of preparation method of efficient, inexpensive active carbocoal low temperature photochemical catalytic oxidation desulphurization and denitration agent is provided, the low temperature that wherein the present invention mentions is normal temperature or a little more than normal temperature, generally lower than 130 ℃ for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent, carry out successively ultrasonic activation by contenting carbon materials such as lignite semi-coke, anthracite or bituminous coal semicokes, acid activation, alkali activation and high-temperature activation and make, wherein said lignite semi-coke, anthracite or bituminous coal semicoke etc. are that 0.4~0.8g/ml, specific area are 10~200m containing the raw-material bulk density of Pd/carbon catalyst 2/ g, carbon content are 70~85%, hydrogen content is 0.5~3.5%, oxygen content is 6~30%, nitrogen content is 0.3~1.8%, moisture is 2~10%, content of ashes is 3~15%, volatile matter content is 6~18%.
Above-mentioned for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent, take the AR such as semicoke and butyl titanate, absolute ethyl alcohol as raw material, described semicoke is obtained to 0.5-40 object semicoke amorphous pellets or shaped granule after screening.
For a preparation method for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent, take semicoke particle as raw material, successively through ultrasonic water activation, acid activation, alkali activation, loaded optic catalyst TiO 2etc. step, finally make the modified semicoke desulphurization and denitration agent that can utilize low temperature photochemical catalytic oxidation.
The above-mentioned preparation method for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent, comprises the following steps:
(1) H that is, 10%~30% by semicoke particle and concentration 2o 2solution, take liquid-solid ratio as 0.5~5 mixing, is processed 0.5~4h at 40-100 ℃ in reactor, and at 110 ℃, dry 1-6h, makes modified semicoke desulphurization and denitration agent semi-finished product;
(2) H that is, 5~85% by step (1) prepared modified semicoke desulphurization and denitration agent semi-finished product and concentration 2sO 4, HNO 3, HCl, HF, H 3pO 4, K 2mnO 4deng acid solution take liquid-solid ratio as 0.5~5 mix, in reflux, at 30~100 ℃, process after 0.5~8h, be washed to neutrality, dry 6h at 110 ℃, afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, activation makes modified semicoke desulphurization and denitration agent semi-finished product at temperature 500-700 ℃;
(3) KOH, NaOH, K that the modified semicoke desulphurization and denitration agent semi-finished product that, step (2) made and concentration are 5~85% 2cO 3, Na 2cO 3, KHCO 3, Na HCO 3, the alkaline solution such as ammoniacal liquor mixes take liquid-solid ratio as 0.5~5, in reflux, at 30~100 ℃, process after 0.5~8h, be washed to neutrality, at 110 ℃ of dry 6h, afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, activation makes modified semicoke desulphurization and denitration agent semi-finished product at temperature 500-700 ℃;
(4), loaded optic catalyst TiO 2preparation: described butyl titanate, absolute ethyl alcohol are raw material, and 30ml butyl titanate is dissolved in 100ml absolute ethyl alcohol, adds a certain amount of diethanol amine after stirring, stirs at a certain temperature 2h, obtains solution;
(5), modified semicoke desulphurization and denitration agent semi-finished product that step (3) is made are impregnated into 6~12h in butyl titanate ethanolic solution, in 110 ℃ of dry 6h, make the agent of finished product modified semicoke desulphurization and denitration.
The above-mentioned preparation method for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent, the corresponding transition-metal Fe of load, Cu, Zn, the nitrate of V, Mn etc. or their mixture again, at 350 ℃-550 ℃, calcine 2-4h, obtain the enhancement mode desulphurization and denitration agent of the transition metal oxides such as Fe2O3, CuO, ZnO, V2O5, Mn2O3 or their mixture.
The above-mentioned preparation method for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent, described finished product modified semicoke desulphurization and denitration agent and molecular sieve NO adsorbent mechanical mixture, make high activity semicoke base optic catalytic oxidation sweetening, denitrfying agent.
The present invention for the advantage of the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent and preparation method thereof is: take amorphous semicoke or graininess semicoke as raw material, through ultrasonic Activation of Hydrogen Peroxide Solution, acid activation, alkali activation, carrying transition metal oxide, photochemical catalyst TiO 2with methods such as Mechanical mixture NO adsorbents, active carbocoal is carried out to the modification of physical arrangement and surface chemical property, finally make the agent of cheap active carbocoal photochemical catalytic oxidation desulphurization and denitration, this desulphurization and denitration agent can be regenerated on the one hand, useless desulphurization and denitration agent can be used as fuel treatment, non-secondary pollution on the other hand.This light adsorption catalyst at low temperatures (≤130 ℃) for removing the NO of the flue gases such as coal-burning power plant, coal-burning boiler and coal-fired furnace x, also can be used for removing contained NO in the ventilating gas of locating to produce in vcehicular tunnel, underground parking, crossing, street etc. x.
The carbon based material wide material sources such as active carbocoal, low price, prepared desulphurization and denitration agent iterative regenerable recycles, and finally also can be used for wastewater treatment or boiler oil, non-secondary pollution.The denitrating technique reaction temperature adopting is normal temperature or a little more than normal temperature (≤130 ℃), and need in reaction, not add Oxidizing and Reducing Agents.The agent of this desulphurization and denitration can be widely used in NO in the flue gases such as coal-burning power plant, coal-burning boiler and coal-fired furnace xremove, also can be used for removing contained NO in the ventilating gas of locating to produce in vcehicular tunnel, underground parking, crossing, street etc. xin gas purification industry in environmental protection industry.
County's body embodiment
Below in conjunction with specific embodiment, the present invention is described in further details;
A kind of it is characterized in that for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent the contenting carbon material such as lignite semi-coke or anthracite, bituminous coal semicoke carries out ultrasonic activation successively, acid activation, alkali activation and high-temperature activation and make.Wherein said lignite semi-coke or anthracite, bituminous coal semicoke etc. are that 0.4~0.8g/mi, specific area are 10~200m containing the raw-material bulk density of Pd/carbon catalyst 2/ g, carbon content are 70~85%, hydrogen content is 0.5~3.5%, oxygen content is 6~30%, nitrogen content is 0.3~1.8%, moisture is 2~10%, content of ashes is 3~15%, volatile matter content is 6~18%.
Its preparation process is as follows: the semicoke that meets above-mentioned physicochemical condition is obtained to 1~40 object particle, the H that semicoke particle and concentration are 2.0%~30% after screening 2o 2solution, take liquid-solid ratio as 0.5~5.0 mixing, is processed 0.5-~4.0h at lower 40-100 ℃ in ultrasonic reaction still, dry 1-6h at 110 ℃; Then the H that is 5.0~85% by above-mentioned steps gained char catalyst semi-finished product and concentration 2sO 4, HNO 3, HCl, HF, H 3pO 4, K 2mnO 4, at 40~90 ℃, process after 0.5~4.0h in the there-necked flask with reflux condensate device take liquid-solid ratio as 0.5~5.0 mixing Deng acid solution, be washed to neutrality, dry 1-6h at 110 ℃; Then by above-mentioned steps gained char catalyst semi-finished product or loaded optic catalyst and transition metal oxide, or proceed alkali activation, with concentration be 5.0~85% KOH, NaOH, K 2cO 3, Na 2cO 3, KHCO 3, NaHCO 3, the alkaline solution such as ammoniacal liquor mixes take liquid-solid ratio as 0.5~5.0, in the there-necked flask device with reflux condensation mode, at 40~100 ℃, processes after 0.5~4h, is washed to neutrality, at 110 ℃ of dry 6h; Then gained char catalyst semi-finished product carrier in above-mentioned steps is carried out to loaded optic catalyst and transition metal oxide: 30ml butyl titanate is dissolved in 100ml absolute ethyl alcohol, after stirring, add a certain amount of diethanol amine, stir at a certain temperature 2h and obtain solution, then a certain amount of semicoke carrier after treatment is added in this solution, place 6~12h, in 110 ℃ of dry 2-6h; Then roasting 2-4h at 350-650 ℃, obtains the char catalyst of loaded optic catalyst, and afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, activation makes support type photocatalysis semicoke denitrating catalyst at temperature 500-700 ℃.By above-mentioned steps gained char catalyst photooxidation catalyst or catalyst of transition metal oxide or/and Mechanical mixture NO adsorbent continues modification.Load Fe 2o 3, CuO, ZnO, V 2o 5in transition metal oxide or they mixture.Or with molecular sieve NO adsorbent mechanical mixture, make high activity semicoke base optic catalytic oxidation sweetening, denitrfying agent.
The active testing of desulphurization and denitration agent carries out in fixed bed reactors, NO xthe reaction temperature that removes be 60 ℃~130 ℃, air speed is 600-2000h -1, in flue gas, gas composition is: NO 340~1600ppm, O 20~10%, steam is 0~12%, and all the other are by N 2balance.Reactor can be by reacting under ultraviolet light and visible light source irradiation.The accumulative total nitre that nitre wherein holds while being 40% for denitration rate holds.
Embodiment 1~5:
4~10 order particle 100g and the 5.0%H that semicoke is obtained after screening 2o 2solution mixes with liquid-solid ratio 1.5, is placed in 500ml round-bottomed flask, and at 80 ℃ of ultrasound environments, reaction keeps 2h, 110 ℃ of dry 2h, then with 45% HNO 3after being 2 mixing by liquid-solid ratio, at 80 ℃, process 2h, be washed to neutral rear 110 ℃ of dry 2h, then after above-mentioned steps gained char catalyst semi-finished product being 2 mixing with 5.0% ammoniacal liquor by liquid-solid ratio, at 40 ℃, process 2h, be washed to neutral rear 110 ℃ of dry 2h, then gained char catalyst semi-finished product in above-mentioned steps are divided into 4 parts, wherein 1 part is designated as A, other 3 parts join 30ml butyl titanate and are dissolved in 100ml absolute ethyl alcohol and at 35 ℃, stir in the solution obtaining after 2h, place 6h, dry 4h at 110 ℃, roasting 2h at 350 ℃, make modified semicoke photocatalysis desulfurization, denitrfying agent precursor, afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, at temperature 500-700 ℃, activation makes modified semicoke photocatalysis desulfurization, denitrfying agent, be designated as B, B is divided into 3 parts, wherein 2 parts with a certain amount of Fe (NO of equi-volume impregnating load 3) 3, dry 3h at 110 ℃, roasting 2h makes finally to make containing Fe at 400 ℃ 2o 34% photocatalysis adsorption desulfurize, denitrfying agent, be designated as C, take a certain amount of C, by C photocatalysis desulphurization and denitration agent and a certain amount of ZSM-5NO adsorption catalyst mechanical mixture, then extruded moulding, obtain photocatalysis adsorption desulfurize, denitrfying agent D.
The active testing condition of semicoke desulphurization and denitration agent is that reaction temperature is 80 ℃, and air speed is 1000h -1, NO780ppm, O 25%, steam is 8.0%, and all the other are by N 2balance, ultraviolet/visible light is irradiated, and final nitre appearance the results are shown in Table 1, and when the calculating that nitre holds is reduced to 40% with denitration rate, the NOx amount of semicoke desulphurization and denitration agent adsorption and conversion accounts for the percentage of semicoke desulphurization and denitration agent weight:
The modified semicoke photocatalysis adsorption desulfurize that the different preparation methods of table 1 and formula obtain, the variation that denitrfying agent nitre holds
Figure BSA00000805734600051
Example 6~7:
By semicoke through screening after obtain 10~40 order particle 100g respectively with distilled water, 20.0% H 20 2solution mixes with liquid-solid ratio 1.5, is placed in 500ml round-bottomed flask, under 150-300w ultrasound environments, keeps 2h, 110 ℃ of dry 2h; Then with 40.0% H 2sO 4solution mixes by liquid-solid ratio 3.0, at 80 ℃, processes 2h, is washed to neutral rear 110 ℃ of dry 2h; Then by above-mentioned steps gained char catalyst semi-finished product and 30.0%Na 2cO 3solution mixes by liquid-solid ratio 3.O, at 100 ℃, processes 1h, is washed to neutral rear 110 ℃ of dry 2h; Then gained char catalyst semi-finished product in above-mentioned steps are dissolved in the solution obtaining after stirring 2h at 40 ℃ in 100ml absolute ethyl alcohol and flood 6h in 30ml butyl titanate, dry 6h at 110 ℃, make modified semicoke photocatalysis adsorption desulfurize, denitrfying agent precursor, afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, activation makes the agent of modified semicoke photocatalysis desulphurization and denitration at temperature 500-700 ℃.
The active testing condition of semicoke desulphurization and denitration agent is that reaction temperature is 70 ℃, and air speed is 800 h -1, NO 780ppm, 0 25%, steam is 5%, and all the other are by N 2balance, ultraviolet/visible light is irradiated respectively, and final nitre appearance the results are shown in Table 2.When the calculating that nitre holds is reduced to 40% with denitration rate, the NOx amount of semicoke desulphurization and denitration agent adsorption and conversion accounts for the percentage of semicoke desulphurization and denitration agent weight.
The impact that in the activation of table 2. high pressure, different medium is held modified semicoke nitre
Figure BSA00000805734600052
Figure BSA00000805734600061
Example 8~13:
To after semicoke screening, obtain 10-40 object particle 100g and 15.0%H 2o 2solution mixes with liquid-solid ratio 1.5, is placed in 500ml round-bottomed flask, in 150~300w ultrasound environments, keeps 2h, 110 ℃ of dry 2h; Then respectively with 40.0%HNO 3solution, 20.0%HNO 3mix with solid-to-liquid ratio 2.0 with 20.0%HCl mixed solution, react 2h at 80 ℃, be washed to neutral rear 110 ℃ of dry 2h, the char catalyst semi-finished product that obtain are designated as respectively G, H; G and H are mixed with liquid-solid ratio 1.5 with 20.0%KOH, 10.0%NaOH and 10.0%KOH mixed solution, certain density MDEA solution respectively, at 100 ℃, keep 1h, be washed to neutral 110 ℃ of dry 2h, afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, activation makes char catalyst semi-finished product and is designated as respectively G-K, G-K-Na, G-M, H-K, H-K-Na, H-M at temperature 500-700 ℃; G-K, G-K-Na, G-M, H-K, H-K-Na, H-M are dissolved in 100ml absolute ethyl alcohol and stir in the solution obtaining after 2h and flood 6h at 40 ℃ respectively at 30ml butyl titanate, 110 ℃ of dry 2h, are designated as G-K-Ti, G-K-Na-Ti, G-M-Ti, H-K-Ti, H-K-Na-Ti, H-M-Ti; Use respectively afterwards a certain amount of Cu (NO of equi-volume impregnating load 3) 2, 350 ℃ of roasting 2h, obtain the char catalyst semi-finished product of Supported CuO 1%, are designated as respectively G-K-Ti-Cu, G-K-Na-Ti-Cu, G-M-Ti-Cu, H-K-Ti-Cu, H-K-Na-Ti-Cu, H-M-Ti-Cu; By above-mentioned char catalyst semi-finished product and ZSM-5 molecular sieve mechanical mixture, extrusion modling again, semicoke photocatalysis adsorption desulfurize, denitrfying agent be can make, G-K-Ti-Cu-Z, G-K-Na-Ti-Cu-Z, G-M-Ti-Cu-Z, H-K-Ti-Cu-Z, H-K-Na-Ti-Cu-Z, H-M-Ti-Cu-Z are designated as.
The active testing condition of semicoke desulphurization and denitration agent is that reaction temperature is 70 ℃, and air speed is 1000h -1, NO 780PPm, 0 25%, steam is 8.0%, and all the other are by N 2balance, ultraviolet/visible light is irradiated, and final nitre appearance the results are shown in Table 3, and when the calculating that nitre holds is reduced to 40% with denitration rate, the NOX amount of semicoke desulphurization and denitration agent adsorption and conversion accounts for the percentage of semicoke desulphurization and denitration agent weight:
The impact that the different soda acid activation methods of table 3. hold semicoke nitre
Figure BSA00000805734600062
Embodiment 13~22:
4~10 order particle 100g and the 10.0%H that semicoke is obtained after screening 2o 2solution mixes with liquid-solid ratio 1.5, is placed in 500ml round-bottomed flask, and at 80 ℃ of ultrasound environments, reaction keeps 2h, 110 ℃ of dry 2h; Then with 30% K 2mnO 4after being 1.5 mixing by liquid-solid ratio, at 60 ℃, process 1h, be washed to neutral rear 110 ℃ of dry 2h; Then after above-mentioned steps gained char catalyst semi-finished product being mixed by liquid-solid ratio 2.5 with 20.0% NaOH solution and 20.0%KOH solution respectively, at 150-300W ultrasound environments and 80 ℃, process 1h, be washed to neutral rear 110 ℃ of dry 2h; And respectively NaOH solution and KOH semicoke after treatment are designated as to E and F.Then gained semicoke E in above-mentioned steps and F catalyst semi-finished product are respectively divided into 2 parts, are designated as respectively E-1, E-2, and F-1, F-2; E-1 and F-1 are joined to 30ml butyl titanate to be dissolved in 100ml absolute ethyl alcohol and at 35 ℃, to stir in the solution obtaining after 2h, place 6h, dry 4h at 110 ℃, roasting 2h at 350 ℃, afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, activation makes the agent of modified semicoke photocatalysis desulphurization and denitration at temperature 500-700 ℃, be designated as E-1-TiO and F-1-TiO; E-2 and F-2 are joined to the TiO of N doping vario-property 2in, obtain E-2-TiO-N and the agent of F-2-TiO-N photochemical catalytic oxidation desulphurization and denitration, continue respectively afterwards a certain amount of Zn (NO of equal-volume load 3) 2, dry 2h at 110 ℃, roasting 3h at 450 ℃, finally makes photocatalysis adsorption desulfurize, denitrfying agent containing ZnO 2.0%, is designated as E-2-TiO-N-Zn and F-2-TiO-N-Zn; Take a certain amount of E-2-TiO-N-Zn and F-2-TiO-N-Zn, respectively with a certain amount of B-1 molecular sieve NO adsorption catalyst mechanical mixture, then extruded moulding, obtain E-2-TiO-N-Zn-Z and F-2-TiO-N-Zn-Z photocatalysis adsorption desulfurize, denitrfying agent.
The active testing condition of semicoke desulphurization and denitration agent is that reaction temperature is 70 ℃, and air speed is 1000h -1, NO 780ppm, O 25%, steam is 8.O%, and all the other are by N 2balance, ultraviolet/visible light is irradiated, and final nitre appearance the results are shown in Table 4, and when the calculating that nitre holds is reduced to 40% with denitration rate, the NOx amount of semicoke desulphurization and denitration agent adsorption and conversion accounts for the percentage of semicoke desulphurization and denitration agent weight:
The modified semicoke photocatalysis adsorption desulfurize that the table 4 each method of different system and formula obtain, the variation that denitrfying agent nitre holds
Figure BSA00000805734600071
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned giving an example; those skilled in the art; in essential scope of the present invention, variation, remodeling, interpolation or the replacement made, all should belong to protection scope of the present invention.

Claims (6)

1. one kind for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent, it is characterized in that: carry out successively ultrasonic activation by contenting carbon materials such as lignite semi-coke, anthracite or bituminous coal semicokes, acid activation, alkali activation and high-temperature activation and make, wherein said lignite semi-coke, anthracite or bituminous coal semicoke etc. are that 0.4~0.8g/ml, specific area are 10~200m containing the raw-material bulk density of Pd/carbon catalyst 2/ g, carbon content are 70~85%, hydrogen content is 0.5~3.5%, oxygen content is 6~30%, nitrogen content is 0.3~1.8%, moisture is 2~10%, content of ashes is 3~15%, volatile matter content is 6~18%.
2. according to claim 1 for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent; it is characterized in that: take the AR such as semicoke and butyl titanate, absolute ethyl alcohol as raw material, described semicoke is obtained to 0.5-40 object semicoke amorphous pellets or shaped granule after screening.
3. for a preparation method for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent, it is characterized in that: take semicoke particle as raw material, successively through ultrasonic water activation, acid activation, alkali activation, loaded optic catalyst TiO 2etc. step, finally make the modified semicoke desulphurization and denitration agent that can utilize low temperature photochemical catalytic oxidation.
4. the preparation method for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent according to claim 3, is characterized in that, comprises the following steps:
(1) H that is, 10%~30% by semicoke particle and concentration 2o 2solution, take liquid-solid ratio as 0.5~5 mixing, is processed 0.5~4h at 40-100 ℃ in reactor, and at 110 ℃, dry 1-6h, makes modified semicoke desulphurization and denitration agent semi-finished product;
(2) H that is, 5~85% by step (1) prepared modified semicoke desulphurization and denitration agent semi-finished product and concentration 2sO 4, HNO 3, HCl, HF, H 3pO 4, K 2mnO 4deng acid solution take liquid-solid ratio as 0.5~5 mix, in reflux, at 30~100 ℃, process after 0.5~8h, be washed to neutrality, dry 6h at 110 ℃, afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, activation makes modified semicoke desulphurization and denitration agent semi-finished product at temperature 500-700 ℃;
(3) KOH, NaOH, K that the modified semicoke desulphurization and denitration agent semi-finished product that, step (2) made and concentration are 5~85% 2cO 3, Na 2cO 3, KHCO 3, NaHCO 3, the alkaline solution such as ammoniacal liquor mixes take liquid-solid ratio as 0.5~5, in reflux, at 30~100 ℃, process after 0.5~8h, be washed to neutrality, at 110 ℃ of dry 6h, afterwards, under 3-25% water vapour content and 2-15% oxygen content condition, activation makes modified semicoke desulphurization and denitration agent semi-finished product at temperature 500-700 ℃;
(4), loaded optic catalyst TiO 2preparation: described butyl titanate, absolute ethyl alcohol are raw material, and 30ml butyl titanate is dissolved in 100ml absolute ethyl alcohol, adds a certain amount of diethanol amine after stirring, stirs at a certain temperature 2h, obtains solution;
(5), modified semicoke desulphurization and denitration agent semi-finished product that step (3) is made are impregnated into 6~12h in butyl titanate ethanolic solution, in 110 ℃ of dry 6h, make the agent of finished product modified semicoke desulphurization and denitration.
5. according to the preparation method for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent described in claim 3 or 4, it is characterized in that: the corresponding transition-metal Fe of load, Cu, Zn, the nitrate of V, Mn etc. or their mixture again, at 350 ℃-550 ℃, calcine 2-4h, obtain the enhancement mode desulphurization and denitration agent of the transition metal oxides such as Fe2O3, CuO, ZnO, V2O5, Mn2O3 or their mixture.
6. the preparation method for the flue gas desulfurization of photochemical catalytic oxidation semicoke base, denitrfying agent according to claim 5, it is characterized in that: described finished product modified semicoke desulphurization and denitration agent and molecular sieve NO adsorbent mechanical mixture, make high activity semicoke base optic catalytic oxidation sweetening, denitrfying agent.
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