CN1327966C - Process for preparing fluorine blended metal oxide catalyst - Google Patents
Process for preparing fluorine blended metal oxide catalyst Download PDFInfo
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- CN1327966C CN1327966C CNB2005100290787A CN200510029078A CN1327966C CN 1327966 C CN1327966 C CN 1327966C CN B2005100290787 A CNB2005100290787 A CN B2005100290787A CN 200510029078 A CN200510029078 A CN 200510029078A CN 1327966 C CN1327966 C CN 1327966C
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Abstract
The present invention relates to a method for preparing a fluorine doping metal oxide catalyst, which comprises the steps that metal oxide precursors and a fluorine doping agent with certain proportion are dissolved in water to obtain a mixed solution; then, a dispersing agent whose total mole amount is from 0 to 3 times of that of the metal oxide precursors and the fluorine doping agent is added to the mixed solution to obtain a gel precursor solution; a catalyst carrier whose weight is from 1 to 100 times of the total weight of the metal oxide precursors and the fluorine doping agent is soaked in the mixed solution or the gel precursor solution; after drying treatment, a catalyst precursor is obtained, and then, the catalyst precursor is calcined in air at the temperature of 100 to 800 DEG C to obtain the fluorine doping metal oxide catalyst. The fluorine doping modified metal oxide catalyst is synthesized by a fluorine doping technology, and fluorine elements are introduced in metal oxide crystals. Prepared fluorine doping metal oxides have strong mercury catalytic oxidation capability. Meanwhile, the preparation method of the present invention is simple and has industrialization application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of fluorine blended metal oxide catalyst, the catalyst that makes can be applicable to flue gas demercuration, belongs to inorganic catalysis material and environmental protection and energy saving technical field.
Background technology
Think after EPA's investigation that the coal-burning power plant is the maximum at present mercury emissions pollution sources that do not have artificial control, consider the huge of power station mercury emission and cause mercury accumulation in the fish body, think that it has necessity of improvement.
Oxidation state mercury is easy to control and does not have global, therefore control mercury technology mainly concentrates on the oxidation state ratio that as far as possible improves mercury in the flue gas at present, no matter be charcoal absorption injection method (ACI), wet flue gas desulfurization (WFGD) method, the clean electric cleaner absorption method of low temperature, bag dust-removing method (FF), catalytic oxidation method (ECO) method, calcium base and oxidant method, mercury catalytic oxidation, selective catalytic reduction (SCR) and non-selective catalytic reduction (SNCR), photochemical method or the like, it shows the oxidation state scale that fine or not key is a mercury.And various factors also is to influence by the form to mercury to carry out to the influential effect of controlling the mercury technology.
The active carbon adsorption technology is that research is maximum at present, and still there are the following problems but it is used in coal fired power plant: (1) performance is unstable, and is very low for the efficiency of plant of burning brown coal; (2) active carbon is very big to the quality influence of flying dust, and the test of american energy office shows: the charcoal absorption injection method makes flying dust not sell as concrete additive; (3) mercury of charcoal absorption is carrying out the research of this respect now to the unknown that influences of environment.If influence very greatly, it may also require to handle as solid waste.Therefore directly adopt the method cost of active carbon adsorption very high.
Other are not high to the system effectiveness of burning brown coal and ub-bituminous coal as wet flue gas desulfurization method, the clean electric cleaner absorption method of low temperature, bag dust-removing method etc., because oxidation state mercury ratio is few in its flue gas.And catalytic oxidation method method, photochemistry, oxidant method and catalytic oxidation rule are directly to utilize various technological means to improve oxidation state mercury ratio.From the economic angle analysis: catalytic oxidation method method, photochemistry, oxidant method require constantly to drop into the energy or chemical reagent governance process, its control mercury cost is suitable with the active carbon injection method, does not meet China's national situation, though U.S. power station also ability do not bear.
Withum(Characterization?of?Coal?Combustion?By-Products?for?theRe-Evolution?of?Mercury?into?Ecosystems。In?Proceedings?of?Air?QualityIII：Mercury，，Trace?Elements，and?Particulate?Matter?Conference；Arlington，VA，September?9-12，2002。) research thinks that coal fired power plant accessory substance (CUBs) be discharged in may and using in waste disposal as the mercury that adsorbs in flying dust and the wet flue gas desulfurization method solid waste once again and cause secondary pollution in the environment.Environmental Protection Agency (EPA), U.S. mechanisms such as (DOE) of Bureau of Energy has begun to pay close attention to and drop into the research that substantial contribution carries out the final home to return to of mercury in the accessory substance of power station, and existing control mercury technology is not considered the influence of accessory substance.
The catalytic oxidation flue gas demercuration is oxidized to mercury oxide and then absorption by using catalysis material with the element mercury in the flue gas, material obtains regeneration by the mercury oxide that adds thermal decomposition absorption, the element mercury that mercury oxide obtains after decomposing is handled by cooling or other chemical reagent, does not have secondary pollution.This method running cost hangs down the mercury emissions rules that also can satisfy the strictness in future and has powerful competitiveness.Catalytic oxidation also has the advantage that traditional absorption method does not have: can carry out the absorption of mercury under hot conditions, thereby be applicable to that clean coal combustion systems of new generation handles as the mercury of the multiple cycle generating system (IGCC) that gasifies etc.
Mercury oxidation catalyst at present commonly used comprise metal oxide, noble metal (Pd, Pt) and other natural materials.Noble metal is easy to poison in the environment of sulphur is arranged, and also there are active problem on the low side in general metal oxide catalyst and natural material.
Summary of the invention
The object of the invention is the problem of and easy poisoning on the low side at the metal oxide activity, and a kind of preparation method of fluorine blended metal oxide catalyst is provided, and it is simple that this preparation method has technology, the advantage that production cost is lower.Mix by metal oxide being carried out fluorine, can improve catalytic oxidation performance and the anti-poisoning capability of metal oxide mercury.
The present invention is achieved by the following technical solutions: with metal oxide precursor and a certain proportion of fluorine dopant mixed solution that obtains soluble in water, the dispersant that adds 0～3 times of metal oxide precursor and fluorine dopant mole total amount again in mixed solution obtains gel precursors solution, with weight is that the catalyst carrier of 1～100 times of metal oxide precursor and fluorine dopant total amount impregnated in above-mentioned mixed solution or the gel precursors solution, obtain catalyst precarsor after dry the processing, calcining obtains fluorine blended metal oxide catalyst in 80 ℃～800 ℃ air atmospheres then.
Method concrete steps of the present invention are as follows:
1, be that the fluorine dopant of 85～99.5% metal oxide precursor and 0.5～15% is soluble in water with percentage by weight, stir and obtain mixed solution, the adding dispersant fully mixes and obtains gel precursors solution in above-mentioned mixed solution, and wherein the mol ratio of dispersant and metal oxide precursor and fluorine dopant total amount is 0～3.
2, be that the catalyst carrier of 1～100 times of metal oxide precursor and fluorine dopant gross weight impregnated in above-mentioned mixed solution or the gel precursors solution with weight, in air, dry naturally or adopt direct mode of heating to obtain catalyst precarsor in 40～100 ℃ of oven dry.Wherein the optimum drying mode is direct drying, and the optimum drying temperature is 50～60 ℃.
3, catalyst precarsor is positioned in the heater under speed is 5～40 ℃/minute condition and is warming up to 80 ℃～800 ℃, under this temperature, keep catalyst precarsor fully being decomposed in 0.5～8 hour, obtain fluorine blended metal oxide catalyst.Wherein optimum temperature rise speed is 9～20 ℃/minute, and best temperature retention time is 0.5～3 hour.
Metal oxide precursor of the present invention comprises that metal nitrate, metal carbonate, metal oxalate, metal acetate and easy pyrolytic produce the salt of metal oxide, can be wherein one or both.
Described fluorine dopant is: HF, F
2Perhaps fluorine-containing inorganic salts.
Described dispersant is that ethylene glycol, glycerine, citric acid, gelatin or other contain the compound of two above hydroxy functional groups.
Described catalyst carrier is each quasi-metal oxides, various rare-earth mineral, all kinds of active carbon and fiber thereof, manually reaches natural molecule sieve, diatomite, silica gel, all kinds of natural crystal, CNT etc., can be wherein one or more.
The present invention adopts the fluorine doping techniques to synthesize fluorine doping vario-property metal oxide catalyst, both in the lattice of metal oxide crystal, mixed fluorine element, mix fluorine element again in its brilliant crack, the content of fluorine accounts for 0.5%～15% in the fluorine blended metal oxide catalyst.The doping meeting functions as follows catalyst like this:
1. form new molecular orbit after the Zp orbital hybridization of the p track of fluorine atom and 0 atom, and being 2P track by 0 atom basically, the valence band of metal oxide constitutes, form the 2P orbital energy level height of new molecular orbit after the p track of fluorine atom and the Zp orbital hybridization of 0 atom, thereby the electronic state that changes metal oxide surface reaches the ability that improves its mercury oxide than original 0 atom.
2. be entrained in and introduce impurity in the crystal, cause defective, thereby improve the catalytic activity of metal oxide.
The evidence fluorine blended metal oxide catalyst is far longer than the metal oxide that does not have doping to the oxidability of mercury, because the doped with fluorine atom has changed the electronic state of catalyst surface, cause the activated centre that the adsorption capacity of product mercury oxide is weakened, stability is improved, metal oxide surface partial oxygen atom is replaced by fluorine atom, has improved its antitoxin performance.
The present invention has substantive distinguishing features and marked improvement, catalytic performance by the fluorine blended metal oxide catalyst of above-mentioned preparation method preparation has obtained improving significantly on the basis of original oxide, anti-simultaneously poisoning performance strengthens, and the preparation method is simple, has the industrial applications prospect.
Description of drawings
Fig. 1 is fluorine blended metal oxide catalyst and the metal oxide catalyst that the does not have doped with fluorine oxidation effectiveness comparison diagram to element mercury.Measuring instrument: AMA254 mercury vapourmeter.
The specific embodiment
The fluorine percentage by weight of fluorine blended metal oxide is all chosen in 0.5%～15% scope in following examples, cited concrete salt does not show to have only them can be used for the preparation of fluorine blended metal oxide in this class, and the salt of other in similar also can be applied to this method.
Embodiment 1
Take by weighing 11.9mg ammonium fluoride and 0.87g cobalt nitrate in the 50ml beaker, add the 25ml deionized water dissolving and obtain mixed solution, take by weighing the 4.6g aluminium oxide and add in the above-mentioned mixed solution, directly heating in baking oven, handled 8 hours down at 50 ℃, evaporative removal moisture obtains catalyst precarsor.Catalyst precarsor is put into Muffle furnace rise to 800 ℃ of following calcination 2 hours, promptly obtain the fluorine doping cobalt metal oxide catalyst of high catalytic activity with 5 ℃/minute speed.
Fixed reaction bed is adopted in the mercury oxidation performance test of fluorine doping cobalt metal oxide catalyst, and fixed reaction bed uses the quartz glass tube of diameter as 6mm, and make at the middle part that the 5mg silica wool is blocked in quartz ampoule.The concentration of mercury uses the mercury osmos tube to control in the gas.Mercury concentration detects uses 4%KMnO
4/ 10%H
2SO
4Solution absorbs element mercury to be measured in the AMA254 mercury vapourmeter then, uses the element mercury concentration in the two light digital display mercury vapourmeter on-line tracing gases of SG-921 simultaneously.Take by weighing 30mg fluorine doping cobalt metal oxide catalyst in fixed adsorbent bed, fixed reaction bed vertically is positioned in the tube type resistance furnace, 250 ℃ of mercury catalytic oxidation performance tests of carrying out 1h.Result of the test is seen Fig. 1, when wherein curve C oF catalyst is fluorine doping cobalt metal oxide catalyst, the ratio of reaction bed outlet element mercury and import element mercury is situation over time, has very high catalytic oxidation ability during the fluorine doping cobalt metal oxide catalyst for preparing as stated above as can be seen.
Embodiment 2
15ml aqueous hydrogen fluoride solution (0.1mol/L) and 1.01g nickel nitrate be dissolved in the 50ml beaker obtain mixed solution, add the 1ml glycerine and obtain gel precursors solution, the 6.4g active carbon is added in the gel precursors solution, in air, placed 10 hours then, filter.The collecting precipitation thing dries naturally in air and obtains catalyst precarsor, catalyst precarsor is put into Muffle furnace calcined 0.5 hour down in 300 ℃, promptly obtains the fluorine doping nickel metal oxide catalyst material of high catalytic activity.
Catalytic activity test is with embodiment 1, and result of the test is seen Fig. 1, and wherein curve N iF is a catalyst when being fluorine doping nickel metal oxide, and the ratio of reaction bed outlet element mercury and import element mercury is situation over time.The nickel metal oxide of doped with fluorine has very strong element mercury oxidability when adsorption temp is 250 ℃ as can be seen.
Embodiment 3
2.7mg sodium fluoride and 0.54g cobalt nitrate and 0.722g copper nitrate be dissolved in the 50ml water obtain mixed solution, adding 0.7g citric acid stirs and obtains gel precursors solution, the 2.5g molecular sieve is put into gel precursors solution, put into baking oven after stirring, slowly dry in 50 ℃ and obtain catalyst precarsor.Catalyst precarsor is put into Muffle furnace be heated to 80 ℃, kept 2 hours, promptly get fluorine doping cobalt copper oxygen composite metal oxide with the speed of 20 ℃/min.This catalyst material of mercury oxidation catalytic activity test shows is higher than the composite metal oxide that does not have doping far away to the oxidation effectiveness of mercury.
Embodiment 4
With 15ml aqueous hydrogen fluoride solution (0.1mol/L) and 5ml concentration is that the ferric oxalate solution of 0.2g/ml is poured into to mix in the 50ml beaker and obtained mixed solution, add and obtain gel precursors solution after 0.3g ethylene glycol stirs, add to be positioned over to dry naturally in the air after the 5.4g active carbon stirs and obtain catalyst precarsor, catalyst precarsor is positioned over the speed with 20 ℃/minute is warmed up to 300 ℃ in the Muffle furnace, keeps cooling after 5 hours promptly to obtain the fluorine doping iron metal oxide catalyst of high catalytic activity.
Embodiment 5
Measure 1.5mg Fluorinse and 10ml manganese nitrate solution in the 50ml beaker, add the dilution of 25ml deionized water and obtain mixed solution, add and obtain gel precursors solution after the 0.6g gelatin fully dissolves, take by weighing 5.6g diatomite and in above-mentioned gel precursors solution, soak, put into air spontaneous combustion drying and obtain catalyst precarsor.Catalyst precarsor is put into Muffle furnace, rise to 350 ℃, kept 2.5 hours, promptly obtain the fluorine doped with manganese metal oxide catalyst of high catalytic activity with 16 ℃/minute speed.
Claims (6)
1, a kind of preparation method of fluorine blended metal oxide catalyst is characterized in that comprising the steps:
1) be that the fluorine dopant of 85～99.5% metal oxide precursor and 0.5～15% is soluble in water with percentage by weight, stir and obtain mixed solution, do not add dispersant in this mixed solution or further add dispersant and fully mix and obtain gel precursors solution, the mol ratio of dispersant and metal oxide precursor and fluorine dopant total amount is 0～3 in above-mentioned mixed solution that obtains or the gel precursors solution, and described metal oxide precursor is one or both in metal nitrate, metal carbonate, metal oxalate, the metal acetate;
2) be that the catalyst carrier of 1～100 times of metal oxide precursor and fluorine dopant gross weight impregnated in above-mentioned mixed solution or the above-mentioned gel precursors solution with weight, in air, dry naturally or adopt direct mode of heating to obtain catalyst precarsor in 40～100 ℃ of oven dry;
3) catalyst precarsor is positioned in the heater under speed is 5～40 ℃/minute condition and is warming up to 80 ℃～800 ℃, under this temperature, keep catalyst precarsor fully being decomposed in 0.5～8 hour, obtain fluorine blended metal oxide catalyst, described metal oxide is cobalt metal oxide, nickel metal oxide, cobalt copper metal oxide, ferroelectric metal oxide or manganese metal oxide.
2, according to the preparation method of the fluorine blended metal oxide catalyst of claim 1, when it is characterized in that preparing catalyst precarsor, the temperature that adopts direct mode of heating drying is 50～60 ℃.
3, according to the preparation method of the fluorine blended metal oxide catalyst of claim 1, it is characterized in that the heating rate described in the step 3 is 9～20 ℃/minute, temperature retention time is 0.5～3 hour.
4, according to the preparation method of the fluorine blended metal oxide catalyst of claim 1, it is characterized in that described fluorine dopant is: HF, F
2Perhaps fluorine-containing inorganic salts.
5, according to the preparation method of the fluorine blended metal oxide catalyst of claim 1, it is characterized in that described dispersant is ethylene glycol, glycerine, citric acid or gelatin.
6,, it is characterized in that described catalyst carrier is for each quasi-metal oxides, various rare-earth mineral, all kinds of active carbon and fiber thereof, manually reach in natural molecule sieve, diatomite, silica gel and the CNT one or more according to the preparation method of the fluorine blended metal oxide catalyst of claim 1.
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| CN102976475B (en) * | 2012-12-20 | 2014-06-04 | 江南大学 | Ozonization water treatment method by taking fluorine-doped manganese dioxide nano composite material as catalyst |
| CN104466202B (en) * | 2014-12-16 | 2016-11-30 | 北京化工大学常州先进材料研究院 | Prepared by the nickel oxide nano porous lithium O for cathode of air battery material of the supported active metals of a kind of Fluorin doped |
| CN110295986A (en) * | 2019-07-03 | 2019-10-01 | 河北工业大学 | A kind of diesel engine exhaust gas treatment device and method |
| CN111346652A (en) * | 2020-04-15 | 2020-06-30 | 同济大学 | Fluorine-doped spinel structure cobaltosic oxide electrocatalytic material and preparation method thereof |
| CN115245832B (en) * | 2021-12-28 | 2023-12-01 | 浙江理工大学 | Preparation method, product and application of fluorine doped metal oxide catalyst |
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| CN1038829A (en) * | 1988-05-16 | 1990-01-17 | 三井石油化学工业株式会社 | From hydrocarbon ils, remove the method for mercury |
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| CN1488423A (en) * | 2003-07-30 | 2004-04-14 | 浙江大学 | Coal-fired mercury discharge control method based on semi-dry process |
| CN1555916A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Preparation method of photocatalytic active fluorine adulterated titanium dioxide nano material |
| CN1555920A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Fluorine adulterated photocatalytic multicrystal material possessing photocatalytic performance under visible light |
| CN1559668A (en) * | 2004-03-11 | 2005-01-05 | 上海交通大学 | Electrochemical regeneration method of flue gas demercury adsorbing material |
-
2005
- 2005-08-25 CN CNB2005100290787A patent/CN1327966C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038829A (en) * | 1988-05-16 | 1990-01-17 | 三井石油化学工业株式会社 | From hydrocarbon ils, remove the method for mercury |
| US5202301A (en) * | 1989-11-22 | 1993-04-13 | Calgon Carbon Corporation | Product/process/application for removal of mercury from liquid hydrocarbon |
| US5607496A (en) * | 1994-06-01 | 1997-03-04 | Brooks Rand, Ltd. | Removal of mercury from a combustion gas stream and apparatus |
| CN1488423A (en) * | 2003-07-30 | 2004-04-14 | 浙江大学 | Coal-fired mercury discharge control method based on semi-dry process |
| CN1555916A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Preparation method of photocatalytic active fluorine adulterated titanium dioxide nano material |
| CN1555920A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Fluorine adulterated photocatalytic multicrystal material possessing photocatalytic performance under visible light |
| CN1559668A (en) * | 2004-03-11 | 2005-01-05 | 上海交通大学 | Electrochemical regeneration method of flue gas demercury adsorbing material |
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