CN101199928B - Process for preparing nanometer gold catalysts adding modification agent - Google Patents
Process for preparing nanometer gold catalysts adding modification agent Download PDFInfo
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- CN101199928B CN101199928B CN2006101681246A CN200610168124A CN101199928B CN 101199928 B CN101199928 B CN 101199928B CN 2006101681246 A CN2006101681246 A CN 2006101681246A CN 200610168124 A CN200610168124 A CN 200610168124A CN 101199928 B CN101199928 B CN 101199928B
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Abstract
The invention is a method for preparing nanometer gold catalyst with modification agent added. Among picolines, triethylene diamine (TEDA), dextrose, dextrose+NaOH, sinistral vitaminC, dextral vitamin C, quinuclidine, quinoxalines or NaCN, one of the agents is mainly used as the modification agent. By adding the modification into supported nanometer gold catalyst, the modification agent can be used for shielding the direct contact between active ingredient and H2O and CO2 or evacuating in an isolated way the function of metal active ingredients, so that nanometer gold catalyst with high activity and stability can be prepared. The nanometer gold catalyst prepared by this method is of good CO-purifying activity and long service life at room temperature.
Description
Technical field
The present invention is a kind of new preparation method, uses the range of application of the nano catalyst that this preparation method obtains to comprise that the colliery self-rescuer, skyscraper Escaping face gruard of anti-CO or other are used to protect device, the CO of CO
2Laser instrument, CO sensor and some special or closed environment in the purification of CO.
Background technology
The CO cleaning catalyst that uses over a long period of time is Hopcalite (hopcalite agent).It 1919 by U.S. John---the common invention in John Hopkins University and University of California, the catalyst of making according to a certain percentage by activated manganese dioxide and cupric oxide.Usually the method for making of Hopcalite catalyst is to adopt sulfuric acid process.The first step is to make activated manganese dioxide, is manganese sulfate fine powder (70 orders are following) is mixed with a spot of water, adds the concentrated sulfuric acid and make manganese sulfate (suspension in 70% sulfuric acid) under constantly stirring.When temperature is 60 ℃,, add granular potassium permanganate (32～50 order) with even speed, the control reaction temperature is between 65～72 ℃, time is about 15～20 minutes, and holding temperature 10 minutes, the water that mixture is injected continuous stirring in the thread mode was hydrolyzed then.Use decantation, at every turn with several washings that decuple sediment 4～5 times, when sulfate radical-free till.In the boil-off liquid impouring of sewage sodium carbonate manganese dioxide suspension, fully stir, add the copper sulphate hot solution again, continue to stir 15 minutes, when being washed till sulfate radical-free till.Follow precipitation, filtration, drying, be broken into powder, extrusion forming.Again in activation furnace, logical dry air is with 270 ℃ (or 300 ℃) activation 2 hours, get final product the Hopcalite catalyst.
The noble metal platinum of load, palladium catalyst also are relatively effectively catalyst of catalysis CO oxidation always.Pt/SnOx[Stark D.S., Haris M.R.J.Phys.E 1988,21:715] be proved to be very effective for a long time to catalysis CO oxidation.Weak point is to give the processing more complicated, and at room temperature, can not play effective function.The method that the preparation of noble metal platinum, palladium catalyst is mainly used is an equi-volume impregnating, and this method is fairly simple, also realizes than being easier on the technology.
Au/Fe
2O
3, the Au catalyst that Au/NiO etc. are oxide carried has very high activity [HarutaM., Yamada N.J.Catal.1989,115:301] to CO oxidation under the room temperature.An Liduns etc. [Chinese patent application publication number CN 00122829] load on gold on single oxide carrier, have prepared can have good catalytic activity under (relative humidity 60%～100%) under environment temperature (10～40 ℃) and the ambient humidity and can satisfy the practical catalyst that requires of breathing mask.If but gold is loaded on single carrier A l
2O
3On, generally can not get having the nano catalyst of low temperature active, if gold is loaded on the independent transition metal oxide, the catalyst that then makes generally has suitable difficulty in realizing industrialized process.Hao Zheng's equality [publication number CN1465427A] adopts coprecipitation to prepare load type nano gold catalyst while catalytic decomposition O at normal temperatures
3And CO.Wang Donghui etc. [publication number CN 1498680A] adopt deposition-precipitation method to prepare the nano catalyst that loads on the complex carrier, and this catalyst has shown the function that very outstanding catalysis CO transforms, and has better industrial application prospect.[publication number CN 03/068389 A1] such as nearest An Liduns utilizes the nanogold particle of catalyst surface and the strong interaction between the spinel structure transition metal oxide, and part gold grain and transition metal formation alloy structure, come steady load type nano Au particle, thus ensure long-term use and storage process in structure and the stability of catalytic activity.The present invention then is from another angle, by adding some dressing agents, utilizes dressing agent can shield active component and H
2O and CO
2Direct contact, or the effect of separate evacuating metal active constituent, the nano catalyst that obtains having greater activity stability.
Summary of the invention
The objective of the invention is to set up the preparation method of a new raising nano catalyst activity stability.The nano catalyst that this method prepares can be 10～100% times in environment temperature-30～50 ℃, relative humidity, has good purification CO activity, has long service life and activity stability.The nano catalyst that this method prepares has the suitability for industrialized production prospect, and its intensity can satisfy actual instructions for use.
Load type nano gold catalyst of the present invention can adopt patent CN 1498680A and the described method of patent 200610000633.8 (application number) to prepare, and also can be the nano catalyst on single carrier or the complex carrier of loading on that adopts that any other method prepares.
The dressing agent of nano catalyst of the present invention is a kind of of picoline, triethylenediamine (TEDA), glucose, glucose+NaOH, L-vitamin C, dextrorotation vitamin C, Kui nuclear alkali, quinoxaline or NaCN.
The adding method of the dressing agent of nano catalyst of the present invention is as follows:
(1) aqueous solution infusion process: it is 0.1%～5% the aqueous solution that dressing agent is mixed with percentage by weight, is impregnated on the load type nano gold catalyst that has prepared according to the method for incipient impregnation;
(2) spray infusion process: it is 0.1%～5% the aqueous solution that dressing agent is mixed with percentage by weight, is sprayed onto equably on the load type nano gold catalyst that has prepared according to the volume required amount of the method for incipient impregnation;
(3) air-flow absorption method: load type nano gold catalyst is placed in the fluidized bed furnace, air communication is crossed put into the heating tube of dressing agent, the dressing agent evaporation is taken away, and feed ebullated bed;
(4) gas phase adsorption method: dressing agent is mixed according to the ratio of percentage by weight 0.1%～5% with load type nano gold catalyst, put into airtight container;
(5) ammonia solution infusion process:, flood according to method (1) then with ammonia spirit place of water solution.
It is 20～100 ℃ that dressing agent prepares temperature required, and be 2～48 hours action time, and the sample that has flooded is through 80～120 ℃ of dryings 2～24 hours, and 200～600 ℃ of roastings 0～8 hour obtain required nano catalyst.
The load capacity of dressing agent is the 0.01-10% of nano catalyst quality.
Nano catalyst of the present invention carries out CO catalytic oxidation performance evaluation on atmospheric fixed bed reactor, raw materials used gas volume consists of: CO:0.2～2%, all the other are air.The CO concentration of turnover reactor is by gas chromatographic analysis, and the minimum detectable range measured value of CO is below the 1ppm.
The heat resistanceheat resistant performance test of catalyst: finished catalyst is placed the drying box air atmosphere, under 120 ℃, heat 72h continuously, the activity change of detecting catalyst.
The anti humility performance experiment of catalyst: finished catalyst is placed reaction tube, unstripped gas successive reaction 72h with water-vapo(u)r saturation under the room temperature, or, handle 72h, the activity change of detecting catalyst continuously with the gas speed that evaluation response is same with the air of water-vapo(u)r saturation under the room temperature.
Nano catalyst of the present invention is under the situation of 50～20000ppm in CO concentration, and the gas volume space velocity is 1 * 10 under normal pressure
3～2.5 * 10
5h
-1The time, reaction temperature is under 20～100% the condition, CO can be catalytically conveted to CO fully for-30～50 ℃, envionmental humidity
2
Compared with the prior art, the present invention has following characteristics:
1. adopt the method for dipping, interpolation dressing agent on existing nano catalyst, preparation has the nano catalyst of fine activity and stability;
2. the activity that has catalysis CO oxidation under the environment temperature, even can be under 20 ℃～40 ℃ temperature, catalysis CO changes CO fully into
2
3. can directly adopt formed porous material, need not processing and forming, and can keep good intensity, be particularly suitable for actual user demand as carrier;
4. technology is simple, lower to the requirement of equipment, and the feasibility of large-scale production is big, has better industrial application prospect.
The specific embodiment
Embodiment 1
The weight ratio that adopts the described preparation method of patent CN 1498680A to obtain is 1: 10: 200 Au/Fe
2O
3/ Al
2O
3Catalyst adopts gas phase adsorption method to add the dressing agent triethylenediamine, and load capacity is 0.3%, and preparation temperature is 100 ℃, and be 12 hours action time, and the sample that has flooded is 120 ℃ of dryings 12 hours, and 300 ℃ of roastings 2 hours obtain nano catalyst.
Consist of CO:0.5% at unstripped gas, O
2: 21%, N
2: 78.5% (percent by volume), gas volume air speed are 10000h
-1, this nanometer gold catalyst catalyzing CO is converted into CO fully
2Permission minimum response temperature be 55 ℃.At 20 ℃, on-line continuous reaction 50 hours, activity does not have obvious downward trend.
Embodiment 2
The weight ratio that adopts the described preparation method of patent CN 1498680A to obtain is 1: 10: 200 Au/Fe
2O
3/ Al
2O
3Catalyst adopts aqueous solution infusion process to add the dressing agent picoline, load capacity be 5%, preparation temperature is 25 ℃, be 12 hours action time, the sample that has flooded is 120 ℃ of dryings 12 hours, 400 ℃ of roastings 1 hour obtain nano catalyst.
Consist of CO:0.5% at unstripped gas, O
2: 21%, N
2: 78.5% (percent by volume), gas volume air speed are 8000h
-1, this nanometer gold catalyst catalyzing CO is converted into CO fully
2Permission minimum response temperature be 60 ℃.At 25 ℃, on-line continuous reaction 30 hours, activity does not have obvious downward trend.
Embodiment 3
The weight ratio that adopts the described preparation method of patent 200610000633.8 (application number) to obtain is 1: 100 Au/Al
2O
3Catalyst adopt to spray infusion process and adds dressing agent dextrorotation vitamin C, and load capacity is 1%, and preparation temperature is 50 ℃, and be 2 hours action time, and the sample that has flooded is 120 ℃ of dryings 12 hours, and 300 ℃ of roastings 2 hours obtain nano catalyst.
Consist of CO:0.5% at unstripped gas, O
2: 21%, N
2: 78.5% (percent by volume), gas volume air speed are 10000h
-1, this nanometer gold catalyst catalyzing CO is converted into CO fully
2Permission minimum response temperature be 43 ℃.At 25 ℃, on-line continuous reaction 50 hours, activity does not have obvious downward trend.
Embodiment 4
The weight ratio that adopts coprecipitation to prepare is 1: 500 Au/CeO
2Catalyst adopts aqueous solution infusion process to add dressing agent glucose, and load capacity is 0.1%, and preparation temperature is 25 ℃, and be 12 hours action time, and the sample that has flooded is 120 ℃ of dryings 12 hours, and 400 ℃ of roastings 1 hour obtain required nano catalyst.
Consist of CO:0.5% at unstripped gas, O
2: 21%, N
2: 78.5% (percent by volume), gas volume air speed are 8000h
-1, this nanometer gold catalyst catalyzing CO is converted into CO fully
2Permission minimum response temperature be 28 ℃.At 25 ℃, on-line continuous reaction 50 hours, activity does not have obvious downward trend.
Embodiment 5
Adopt the prepared catalyst of example 4, be placed in the drying box in the air atmosphere, at 120 ℃ of heating 72h continuously down, adopt example 4 described conditions to estimate then, this nanometer gold catalyst catalyzing CO is converted into CO fully
2Permission minimum response temperature be 32 ℃.At 25 ℃, this catalyst still can be converted into CO by the CO of catalysis more than 95% fully
2
Embodiment 6
Adopt the prepared catalyst of example 4, be placed in the reaction tube, continuously by beds 72h, adopt example 4 described conditions to estimate with the unstripped gas of water-vapo(u)r saturation under the room temperature then, this nanometer gold catalyst catalyzing CO is converted into CO fully
2Permission minimum response temperature be 38 ℃.At 25 ℃, this catalyst still can be converted into CO by the CO of catalysis more than 90% fully
2
Claims (1)
1. a preparation method who adds the nano catalyst of dressing agent is characterized in that the weight ratio that adopts coprecipitation to prepare is 1: 500 Au/CeO
2Catalyst adopts aqueous solution infusion process to add dressing agent glucose, and load capacity is 0.1%, and preparation temperature is 25 ℃, and be 12 hours action time, and the sample that has flooded is 120 ℃ of dryings 12 hours, and 400 ℃ of roastings 1 hour obtain required nano catalyst;
In the feed gas volume percentage composition is CO:0.5%, O
2: 21%, N2:78.5%, the gas volume air speed is 8000h
-1, this nanometer gold catalyst catalyzing CO is converted into CO fully
2Permission minimum response temperature be 28 ℃; At 25 ℃, on-line continuous reaction 50 hours, activity does not have obvious downward trend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101681246A CN101199928B (en) | 2006-12-15 | 2006-12-15 | Process for preparing nanometer gold catalysts adding modification agent |
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|---|---|---|---|
| CN2006101681246A CN101199928B (en) | 2006-12-15 | 2006-12-15 | Process for preparing nanometer gold catalysts adding modification agent |
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|---|---|
| CN101199928A CN101199928A (en) | 2008-06-18 |
| CN101199928B true CN101199928B (en) | 2010-09-15 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498680A (en) * | 2002-11-08 | 2004-05-26 | 中国人民解放军63971部队 | Catalyzer for purifying CO under certain environmental condition |
| CN1745879A (en) * | 2004-09-09 | 2006-03-15 | 中国科学院兰州化学物理研究所 | Carbon monoxide oxidation and selective oxidation Catalysts and its preparation method |
-
2006
- 2006-12-15 CN CN2006101681246A patent/CN101199928B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1498680A (en) * | 2002-11-08 | 2004-05-26 | 中国人民解放军63971部队 | Catalyzer for purifying CO under certain environmental condition |
| CN1745879A (en) * | 2004-09-09 | 2006-03-15 | 中国科学院兰州化学物理研究所 | Carbon monoxide oxidation and selective oxidation Catalysts and its preparation method |
Non-Patent Citations (5)
| Title |
|---|
| J.L. Margitfalvi et al..Au/MgO catalysts modified with ascorbic acid for lowtemperature CO oxidation.Catalysis Today72.2002,72157-169. * |
| 王东辉等.纳米金催化剂上CO 低（常）温氧化的研究.化学进展14 5.2002,14(5),360-367. |
| 王东辉等.纳米金催化剂上CO 低(常)温氧化的研究.化学进展14 5.2002,14(5),360-367. * |
| 齐世学等.负载型金催化剂.化学通报 11.2002,(11),733-741. |
| 齐世学等.负载型金催化剂.化学通报 11.2002,(11),733-741. * |
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