CN1326620C - Process for preparing bromine blended metal oxide catalyst - Google Patents
Process for preparing bromine blended metal oxide catalyst Download PDFInfo
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- CN1326620C CN1326620C CNB2005100290819A CN200510029081A CN1326620C CN 1326620 C CN1326620 C CN 1326620C CN B2005100290819 A CNB2005100290819 A CN B2005100290819A CN 200510029081 A CN200510029081 A CN 200510029081A CN 1326620 C CN1326620 C CN 1326620C
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Abstract
The present invention relates to a method for preparing a bromine doping metal oxide catalyst, which comprises the steps that metal oxide precursors and a bromine 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 bromine 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 bromine 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 a temperature of 100 to 800 DEG C to obtain the bromine doping metal oxide catalyst. The bromine doping modified metal oxide catalyst is synthesized by a bromine doping technology, and bromine elements are introduced in metal oxide crystals. Prepared bromine 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 bromine 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 objective of the invention is to the problem at the active on the low side and easy poisoning of metal oxide, a kind of preparation method of bromine blended metal oxide catalyst is provided, it is simple that this preparation method has technology, the advantage that production cost is lower.Mix by metal oxide being carried out bromine, 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 bromine adulterant mixed solution that obtains soluble in water, the dispersant that adds 0～3 times of metal oxide precursor and bromine adulterant 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 bromine adulterant total amount impregnated in above-mentioned mixed solution or the gel precursors solution, obtain catalyst precarsor after dry the processing, calcining obtains bromine blended metal oxide catalyst in 100 ℃～800 ℃ air atmospheres then.
Method concrete steps of the present invention are as follows:
1, be that the bromine adulterant of 68～99.9% metal oxide precursor and 0.1～32% 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 bromine adulterant total amount is 0～3.
2, be that the catalyst carrier of 1～100 times of metal oxide precursor and bromine adulterant 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 0.5～8 hour, obtain bromine 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 bromine adulterant is: HBr, Br
2, or brominated 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 bromine doping techniques to come synthetic bromide doping vario-property metal oxide catalyst, both mixes bromo element in the lattice of metal oxide crystal, mixes bromo element again in its brilliant crack, and the content of bromine accounts for 0.1～32% in the bromine 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 bromine atoms 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 bromine atoms 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 bromine blended metal oxide catalyst is far longer than the metal oxide that does not have doping to the oxidability of mercury, because the doping bromine atoms 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 bromine atoms, has improved its antitoxin performance.
The present invention has substantive distinguishing features and marked improvement, catalytic performance by the bromine 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 bromine blended metal oxide catalyst and the bromine that do not mix to element mercury.Measuring instrument: AMA254 mercury vapourmeter.
The specific embodiment
The bromine percentage by weight of bromine blended metal oxide is all chosen in 0.1～32% scope in following examples, cited concrete salt does not show to have only them can be used for the preparation of bromine 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 bromide and 0.727g cobalt nitrate in the 50ml beaker, add the 25ml deionized water dissolving and obtain mixed solution, take by weighing the 3.6g aluminium oxide and put into mixed solution immersion filtration after 6 hours, be placed on directly heating in the baking oven, drying is after 8 hours down at 60 ℃, and it is standby to obtain the catalyst precarsor placement.Catalyst precarsor is placed Muffle furnace, rise to 400 ℃ of calcination 2 hours, promptly obtain the bromine 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 bromine 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 bromine 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 not mix under the cobalt oxide situation of bromine, the ratio of reaction bed outlet element mercury and import element mercury is situation over time, curve C oBr is a catalyst when being bromine 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 bromine of mixing as can be seen is far longer than the cobalt oxide of the bromine that do not mix to the oxidability of mercury when adsorption temp is 250 ℃.
Embodiment 2
15ml aqueous solution of hydrogen bromide (0.1mol/L) and 1.01g nickel nitrate be dissolved in the 50ml beaker obtain mixed solution, add and to obtain gel precursors solution after 0.3g ethylene glycol stirs, add the 5.4g active carbon and fully stir and be placed in the air air dry and filtered in 10 hours and obtain bromine doping nickel metal oxide catalyst precursors.The bromine speed that the nickel metal oxide catalyst precursors is positioned in the Muffle furnace with 20 ℃/minute of mixing is warmed up to 300 ℃ of calcinings 1.5 hours, promptly obtains the bromine doping nickel metal oxide catalyst of high catalytic activity.
In the catalytic activity test with embodiment 1, result of the test is seen Fig. 1, wherein curve N i is that catalyst is not mix under the nickel oxide situation of bromine, the ratio of reaction bed outlet element mercury and import element mercury is situation over time, curve N iBr is a catalyst when being bromine doping nickel oxide, and the ratio of reaction bed outlet element mercury and import element mercury is situation over time.Bromine doping nickel metal oxide catalyst is far longer than the oxidability of mercury when adsorption temp is 250 ℃ does not as can be seen have nickel oxide.
Embodiment 3
3.7mg sodium bromide and 0.464g cobalt nitrate and 0.602g copper nitrate be dissolved in the 50ml water obtain mixed solution, in mixed solution, add the 0.9g citric acid, obtain gel precursors solution after stirring, the 2.5g molecular sieve is joined in the gel precursors solution, put into baking oven after stirring and obtain bromine doping cobalt copper oxygen composite metal oxide precursor in 60 ℃ of oven dry.Place Muffle furnace to be heated to 600 ℃ the bromine cobalt copper oxygen composite metal oxide precursor that mixes, kept 2 hours, promptly get bromine 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
Take by weighing 0.23mlBr
2With the 2.24g copper nitrate in the 50ml beaker, add the 35ml deionized water dissolving and obtain mixed solution, add the 1ml glycerine, obtain gel precursors solution after stirring, take by weighing the 0.43g CNT and in above-mentioned solution, soak filtration after 8 hours, it is interior in 60 ℃ times dry 5 hours to be placed on baking oven, and evaporative removal moisture obtains catalyst precarsor.Then catalyst precarsor is placed in the Muffle furnace, rises to 540 ℃ with 35 ℃/minute speed and kept 8 hours, promptly obtain the bromine copper doped metal oxide catalyst of high catalytic activity.
Embodiment 5
Measure 1.5ml hydrogen bromide solution and 12ml 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 0.4g gelatin fully dissolves, take by weighing 8.4g 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 450 ℃, kept 4 hours, promptly obtain the bromine doped with manganese metal oxide catalyst of high catalytic activity with 26 ℃/minute speed.
Claims (6)
1, a kind of preparation method of bromine blended metal oxide catalyst is characterized in that comprising the steps:
1) be that the bromine adulterant of 68～99.9% metal oxide precursor and 0.1～32% 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 bromine adulterant 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 bromine adulterant 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 0.5～8 hour, obtain bromine blended metal oxide catalyst, described metal oxide is cobalt metal oxide, nickel metal oxide, cobalt copper metal oxide, copper metal oxide or manganese metal oxide.
2, according to the preparation method of the bromine 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 bromine 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 bromine blended metal oxide catalyst of claim 1, it is characterized in that described bromine adulterant is: HBr, Br
2, or brominated inorganic salts.
5, according to the preparation method of the bromine 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 bromine blended metal oxide catalyst of claim 1.
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| CN1326620C true CN1326620C (en) | 2007-07-18 |
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| CN103285805B (en) * | 2013-06-18 | 2015-09-23 | 广州博能能源科技有限公司 | Mercury removal agent and preparation method thereof |
| CN104474888B (en) * | 2014-12-03 | 2016-04-20 | 华中科技大学 | A kind of processing method of elemental mercury from coal-fired flue gas |
| CN105126880B (en) * | 2015-07-24 | 2018-03-16 | 广州博能能源科技有限公司 | A kind of mercury removal agent and preparation method thereof |
Citations (6)
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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 |
| 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 |
| CN1556151A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Preparation method of photocatulyzed active bromine adulerated titanium dioxide nano-material |
| 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 CNB2005100290819A patent/CN1326620C/en not_active Expired - Fee Related
Patent Citations (6)
| 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 |
| CN1556151A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Preparation method of photocatulyzed active bromine adulerated titanium dioxide nano-material |
| 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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