CN1748867A - Process for preparing chlorine blended metal oxide catalyst - Google Patents
Process for preparing chlorine blended metal oxide catalyst Download PDFInfo
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- CN1748867A CN1748867A CN 200510029080 CN200510029080A CN1748867A CN 1748867 A CN1748867 A CN 1748867A CN 200510029080 CN200510029080 CN 200510029080 CN 200510029080 A CN200510029080 A CN 200510029080A CN 1748867 A CN1748867 A CN 1748867A
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Abstract
The preparation process of chlorine doped metal oxide catalyst includes the following steps: dissolving metal oxide precursor and chlorine dopant in certain ratio in water to obtain mixture solution; adding dispersant in 0-3 times the molar amount of metal oxide precursor and chlorine dopant into the solution to obtain gel precursor solution; soaking catalyst carrier in 1-100 times the weight of metal oxide precursor and chlorine dopant inside the gel precursor solution and drying to obtain catalyst precursor; and calcining in air atmosphere at 100-800 deg c to obtain the chlorine doped metal oxide catalyst. The chlorine doped metal oxide catalyst has very high mercury catalytically oxidizing capacity, and has simple preparation process and industrial application foreground.
Description
Technical field
The present invention relates to a kind of preparation method of chlorine 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 chlorine 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 chlorine, 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 chlorine dopant mixed solution that obtains soluble in water, the dispersant that adds 0～3 times of metal oxide precursor and chlorine 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 chlorine dopant total amount impregnated in above-mentioned mixed solution or the gel precursors solution, obtain catalyst precarsor after dry the processing, calcining obtains chlorine blended metal oxide catalyst in 100 ℃～800 ℃ air atmospheres then.
Method concrete steps of the present invention are as follows:
1, be that the chlorine dopant of 76～99.9% metal oxide precursor and 0.1～24% 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 chlorine dopant total amount is 0～3.
2, be that the catalyst carrier of 1～100 times of metal oxide precursor and chlorine 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 100 ℃～800 ℃, under this temperature, keep catalyst precarsor fully being decomposed in 0.5～5 hour, obtain chlorine 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 chlorine dopant is: HCl, Cl
2, HClO
3, HClO or chloride 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 chlorine doping techniques to synthesize chlorine doping vario-property metal oxide catalyst, both in the lattice of metal oxide crystal, mixed the chlorine element, mix the chlorine element again in its brilliant crack, the content of chlorine accounts for 0.1%～24% in the chlorine 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 chlorine atom and O atom, and being 2P track by the O 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 chlorine atom and the Zp orbital hybridization of O atom, thereby the electronic state that changes metal oxide surface reaches the ability that improves its mercury oxide than original O atom.
2. be entrained in and introduce impurity in the crystal, cause defective, thereby improve the catalytic activity of metal oxide.
The evidence chlorine blended metal oxide catalyst is far longer than the metal oxide that does not have doping to the oxidability of mercury, because doping chlorine 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 the chlorine atom, has improved its antitoxin performance.
The present invention has substantive distinguishing features and marked improvement, catalytic performance by the chlorine 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 the oxidation effectiveness comparison diagram of the metal oxide catalyst of the chlorine blended metal oxide catalyst and the chlorine that do not mix to element mercury.Measuring instrument: AMA254 mercury vapourmeter.
The specific embodiment
The chlorine percentage by weight of chlorine blended metal oxide is all chosen in 0.1%～24% scope in following examples, cited concrete salt does not show to have only them can be used for the preparation of chlorine 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 33.9mg ammonium chloride and 0.727g cobalt nitrate in the 50ml beaker, add the 25ml deionized water dissolving, obtain mixed solution, take by weighing the 3.6g aluminium oxide and soaks in above-mentioned solution that filtration obtains catalyst precarsor after 6 hours.With catalyst precarsor in baking oven in 60 ℃ dry 8 hours down, evaporative removal moisture obtains dried catalyst precarsor.In Muffle furnace, rise to 100 ℃ then, kept 0.5 hour, promptly obtain the chlorine 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 chlorine 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.The concentration of element mercury is used 4%KMnO
4/ 10%H
2SO
4Solution absorbs to be measured in the AMA254 mercury vapourmeter then, uses the element mercury concentration in the two online detection gases of light digital display mercury vapourmeter of SG-921 simultaneously.Take by weighing 30mg chlorine 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, wherein curve C o is that catalyst is when being cobalt oxide, the ratio of reaction bed outlet element mercury and import element mercury is situation over time, curve C oCl is a catalyst when being chlorine doping cobalt metal oxide catalyst, and the ratio of reaction bed outlet element mercury and import element mercury is situation over time.The cobalt oxide of chlorine of mixing as can be seen is far longer than the cobalt oxide of the chlorine that do not mix to the oxidability of mercury when adsorption temp is 250 ℃.
With 15ml hydrochloride aqueous 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 chlorine doping iron metal oxide catalyst of high catalytic activity.
Embodiment 3
With 3.7mg HClO
3Be dissolved in the 50ml water with 0.464g cobalt acetate and 0.602g copper carbonate, add the 0.9g citric acid, obtain gel precursors solution after stirring, in above-mentioned precursor solution, add the 3.5g molecular sieve, put into baking oven then in 100 ℃ of oven dry, the cobalt copper oxygen composite metal oxide precursor of the chlorine that obtains mixing.The cobalt copper oxygen composite metal oxide precursor of doping chlorine is positioned in the Muffle furnace is heated to 800 ℃ with 40 ℃/minute speed and kept 2 hours, promptly get chlorine doping cobalt copper oxygen composite metal oxide.
The catalytic activity test is with embodiment 1, result of the test is seen Fig. 1, wherein curve C oCu is that catalyst is not for having under the cobalt copper oxygen composite metal oxide situation, the ratio of reaction bed outlet element mercury and import element mercury concentration is situation over time, curve C oCuCl is a catalyst when being chlorine doping cobalt copper oxygen composite metal oxide, and the ratio of reaction bed outlet element mercury and import element mercury concentration is situation over time.The cobalt copper oxygen composite metal oxide of chlorine of mixing as can be seen is far longer than the oxidability of mercury when adsorption temp is 250 ℃ does not have cobalt copper oxygen composite metal oxide.
Embodiment 4
Take by weighing 0.4mlHClO and 1.24g nickel nitrate in the 50ml beaker, add the 35ml deionized water dissolving and obtain mixed solution, add the 0.45g glycerine, obtain gel precursors solution after stirring, take by weighing the 0.6g CNT and soaks in above-mentioned solution that filtration obtains catalyst precarsor after 6 hours.With catalyst precarsor in baking oven in 60 ℃ dry 3 hours down, evaporative removal moisture obtains dried catalyst precarsor.In Muffle furnace, rise to 400 ℃ with 5 ℃/minute speed and kept 2 hours then, promptly obtain the chlorine doping nickel metal oxide catalyst of high catalytic activity.
Embodiment 5
Measure 1.5ml hydrogen chloride solution 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 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 chlorine doped with manganese metal oxide catalyst of high catalytic activity with 16 ℃/minute speed.
Claims (7)
1, a kind of preparation method of chlorine blended metal oxide catalyst is characterized in that comprising the steps:
1) be that the chlorine dopant of 76～99.9% metal oxide precursor and 0.1～24% 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 chlorine dopant total amount is 0～3;
2) be that the catalyst carrier of 1～100 times of metal oxide precursor and chlorine 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 100 ℃～800 ℃, under this temperature, keep catalyst precarsor fully being decomposed in 0.5～5 hour, obtain chlorine blended metal oxide catalyst.
2, according to the preparation method of the chlorine 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 chlorine blended metal oxide catalyst of claim 1, it is characterized in that the programming 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 chlorine blended metal oxide catalyst of claim 1, it is characterized in that described metal oxide precursor be metal nitrate, metal carbonate, metal oxalate, metal acetate and easily pyrolytic produce in the salt of metal oxide one or both.
5, according to the preparation method of the chlorine blended metal oxide catalyst of claim 1, it is characterized in that described chlorine dopant is: HCl, Cl
2, HClO
3, HClO or chloride inorganic salts.
6, according to the preparation method of the chlorine blended metal oxide catalyst of claim 1, it is characterized in that described dispersant is ethylene glycol, glycerine, citric acid, gelatin or the compound that contains two above hydroxy functional groups.
7,, 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, all kinds of natural crystal and the CNT one or more according to the preparation method of the chlorine blended metal oxide catalyst of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110227507A (en) * | 2019-06-17 | 2019-09-13 | 浙江工业大学 | A kind of ultralow mercury catalyst of high stability and its preparation method and application |
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| ES2034626T3 (en) * | 1988-05-16 | 1993-04-01 | Mitsui Petrochemical Industries, Ltd. | A METHOD OF ELIMINATION OF MERCURY AND / OR MERCURY COMPOUNDS FROM A HYDROCARBON OIL. |
| 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 |
| CN1219580C (en) * | 2003-07-30 | 2005-09-21 | 浙江大学 | Coal-fired mercury discharge control method based on semi-dry process |
| CN1265876C (en) * | 2003-12-30 | 2006-07-26 | 上海交通大学 | Preparation method of photo catalytic active chlorine adulterated titanium dioxide nano material |
| CN1263539C (en) * | 2004-03-11 | 2006-07-12 | 上海交通大学 | Electrochemical regeneration method of flue gas demercury adsorbing material |
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| CN110227507A (en) * | 2019-06-17 | 2019-09-13 | 浙江工业大学 | A kind of ultralow mercury catalyst of high stability and its preparation method and application |
| CN110227507B (en) * | 2019-06-17 | 2021-12-07 | 浙江工业大学 | High-stability ultralow-mercury catalyst and preparation method and application thereof |
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