CN1020150C - Platinum/zeolite organic waste gas purifying catalyst and preparing process thereof - Google Patents
Platinum/zeolite organic waste gas purifying catalyst and preparing process thereof Download PDFInfo
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- CN1020150C CN1020150C CN 88100268 CN88100268A CN1020150C CN 1020150 C CN1020150 C CN 1020150C CN 88100268 CN88100268 CN 88100268 CN 88100268 A CN88100268 A CN 88100268A CN 1020150 C CN1020150 C CN 1020150C
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Abstract
The present invention relates to a platinum/zeolite organic waste gas purifying catalyst which is prepared from a natural zeolite as a carrier, and platinum as a main active component. The purifying catalyst is characterized in that the natural silky zeolite as the carrier is modified into one of ammonium type, sodium type, potassium type and calcium type through ion exchange; the Pt content is from 0.02 to 0.03% (weight ratio); the catalyst can also contain one or more than one of oxides of transitional metal: nickel, manganese and vanadium as a cocatalyst. The catalyst has better purifying effect on industrial exhaust waste gas containing CO, hydrocarbons and oxygen-containing derivatives thereof. Under the conditions that concentration is (3 to 6) X 10 to the power of 3 mg/cube meter, airspeed is from 4500 to 40000 H to minus one, and inlet temperature of reaction gas is from 150 to 280 DEG C, the purifying rate is greater than or equal to 98%. The present invention has the characteristics of low Pt content, high activity, low reaction temperature, wide adaptation range of space velocity, simple preparation process, long service life, etc.
Description
The present invention relates to platiniferous catalyst for purifying organic waste gas and preparation method thereof.
Chemical industry, light industry, coating, the organic exhaust gas that industries such as printing are discharged is one of atmosphere primary pollution source, and as paint, the organic exhaust gas that painting production is discharged contains benzene, toluene, dimethylbenzene, cresols, ethyl acetate etc., phthalic anhydride production process discharge tail gas contains phthalic anhydride, cis-butenedioic anhydride, carbon monoxide and some other intermidate oxides, have strong impulse, tearing property, directly discharging causes serious pollution to environment.The processing method that adopts has WATER-WASHING METHOD, hot burning method and catalytic burning method at present.The catalytic burning method is the important method of cleaning organic waste gas, and the key of this method is to work out function admirable and the low catalyst of cost.
Catalyst for application on the industrial production adopts noble metal platinum mostly at present, and palladium is main active constituent, and bullion content is generally the some thousandths of order of magnitude, as Japan Patent; Clear 60-22930 catalyst contains pt, and pd respectively is 0.05mg/cm
2, clear 58-81247 catalyst, containing the pt amount is 0.2～0.3%; The catalyst platinum containing amount that shanghai food industry tin graphed sheet factory uses from the purifier cu-150 that Japan introduces is 2 grams per liters, the FCC-3188 type catalyst that strain state communication element factory produces, platinum containing amount is 0.1% etc., and above-mentioned catalyst is because the platinum containing amount height, and is difficult for applying.
For reducing the content of noble metal, improve activity of such catalysts, reduce cost, it is carrier that Hangzhou University provided with the natural mordenite zeolite since 1981, is the NZP catalyst series of main active component with the noble metal platinum, and its platinum content is 0.02-0.03%, this catalyst series has active high, characteristics such as the life-span is long, and cost is low have obtained favorable social and economic benefits through commercial Application.(referring to chemical industry environmental protection, nineteen eighty-twos 2 roll up, petrochemical industry, 1984 13 volumes, petrochemical industry, 1985 14 volumes).
The present invention is on the basis of above-mentioned catalyst, and several Catalysts and its preparation methods that can effectively purify various hydrocarbon-containifirst and containing oxygen derivative waste gas thereof are provided.
Organic exhaust gas catalyst provided by the invention, be being carrier through the natural mordenite zeolite of modification, carrier after the modification can be the ammonium type, the sodium type, potassium type, calcium type etc., with platinum is main active component, also can contain in the oxides such as transiting metal nickel, manganese, vanadium one or more for co-catalyst, its active component platinum content is vehicle weight 0.02-0.03%, co-catalyst transition metal oxide NiO.MnO
2, V
2O
5, content is respectively the 0.03-0.05% of vehicle weight, 0.05-0.15%, 0.03-0.1%.
Preparation of catalysts method of the present invention is: platinum is dissolved in chloroazotic acid, and adding concentrated ammonia liquor, to be transformed into the platinum ammoniacal liquor standby; Natural mordenite zeolite added contain ammonium, sodium, potassium, a kind of salting liquid in the calcium salt, preferably corresponding chloride, by solid-to-liquid ratio 1: the 1.2-2(volume ratio), heating was boiled 4-5 hour, and modification becomes the ammonium type, sodium type, potassium type, ca-form zeolite carrier.A kind of method is in above-mentioned platinum ammoniacal liquor exchange absorption platinum with modified zeolite carrier direct impregnation, also having a kind of method is the Zeolite support of modification to be added contain transiting metal nickel. manganese. after the solution exchange absorption load of one or more salt of vanadium, impregnated in above-mentioned platinum ammoniacal liquor exchange absorption platinum again, behind the exchange absorption platinum, but convection drying, activation, also can add after the reducing agent reduction dry again, activation catalyst of the present invention.
The Main Feature of catalyst of the present invention is:
1. processing object: to containing CO, the industrial discharge waste gas of hydro carbons and containing oxygen derivative thereof has good clean-up effect.
2. active high.Reaction temperature is low, and air speed accommodation is wide, to benzene, and toluene, dimethylbenzene, naphthalene, phthalic anhydride, cis-butenedioic anhydride, cyclohexene, cyclohexanone, acetone, metacresol, ethanol, butanols, ethyl acetate, reactants such as acetic acid are in dense (3～6) * 10
3Mg/m
3, air speed 4500～4 * 10
4h
-1, 150～280 ℃ of reaction gas inlet temperatures, purifying rate 〉=98%.
3. antitoxin performance is good, for pb, and p, As, Sb, S.H
2O, CO
2Deng poisonous substance in sizable concentration range, activity is not had obvious influence.
4. good heat resistance can bear 800 °～900 ℃ high temperature, short times and impact, and activity is not had obvious influence.
5. activity stability is good, has several catalyst to be extensive use of in factory, and what have reaches more than 5 years, is still continuing use.
Embodiment 1
By above-mentioned preparation method, with the platinum aqua regia dissolution, add concentrated ammonia liquor and be transformed into platinum ammonium complex ion solution, it is standby to get 700 milliliters of platinum ammoniacal liquors that contain 0.2 gram platinum; Take by weighing the natural mordenite zeolite of 1000 gram 3-5mm granularities, immersion 1500 restrains in the aqueous solution that contains 150 gram ammonium chlorides carries out ion-exchange, heating is boiled, emit mother liquor after 2 hours, add again 1000 the gram contain 100 the gram ammonium chlorides the aqueous solution carry out the ion-exchange second time, emit mother liquor after 2 hours, be washed to no Cl
-Ion changes drying in 120 ℃ of baking ovens over to, gets ammonium type Zeolite support; This carrier is immersed 1500 again and restrain in the mixed aqueous solution that contains 30 gram manganese sulfates, 10 gram nickelous sulfates, nickel-loaded, manganese ion as co-catalyst, are washed to no SO
- 4Ion, above-mentioned standby platinum ammonia solution is added load nickel, on the ammonium type Zeolite support of manganese, under 95-100 ℃ of temperature, exchange absorption platinum 4-5 hour changes in 120 ℃ of baking ovens dry, be raised to 250 ℃ of insulations 1 hour by room temperature, be warmed up to again in the 450-500 ℃ of air atmosphere and activate 4-5 hour.This catalyst platinum containing amount is 0.02% of a vehicle weight, contains the NiO amount for vehicle weight 0.04%, contains MnO
2Amount is 0.07% of vehicle weight.
This activity of such catalysts is to reactant concentration 2000-6000mg/m such as benzene, dimethylbenzene, ethyl acetate
3, air speed 10000～15000h
-1, 100 milliliters of catalyst loading amounts, 180～250 ℃ of inlet temperatures, conversion ratio 〉=98%.
Embodiment 2
Press embodiment 1 described preparation method, getting the platinum ammoniacal liquor is 800 milliliters, platiniferous 0.25 gram, the modenite amount is 1000 grams, and modified-salt adopts sodium-chloride water solution, exchanges 10% concentration sodium chloride solution, 1500 grams for the first time, be exchanged for for the second time 10% concentration sodium chloride solution, 1200 grams, add and contain 0.46 gram V
2O
5The oxalic acid aqueous solution load cocatalyst, the catalyst platinum containing amount for preparing is 0.025% of a vehicle weight, contains V
2O
5Amount is carrier amount 0.046%.This catalyst activity is: to reactants such as the bitter edible plant, phthalic anhydride, cis-butenedioic anhydride, 100 milliliters of catalyst loading amounts, 180～250 ℃ of gasinlet temperatures, conversion ratio 〉=98%.
Embodiment 3
Press embodiment 1 described preparation method, get 700 milliliters of platinum ammoniacal liquors, platiniferous 0.3 gram is standby, and sodium-chloride water solution 1500 grams that the natural mordenite zeolite beads of getting 1000 gram φ, 3～5mm add 15% concentration carry out ion-exchanged, 3 hours swap times, are washed to no Cl
-Ion, transfer to 120 ℃ of oven dryings, standby platinum ammoniacal liquor is added on above-mentioned bead carries out ion-exchange absorption platinum, emit mother liquor after 2 hours, carry out electronation for 500 milliliters with 5% formalin, emit stoste after 2 hours, bead is transferred to oven drying, is activated, this activity of such catalysts component platinum content be carrier heavy 0.03%.
This activity of such catalysts is the reaction of paraxylene, concentration (3-5) * 10
3Mg/m
1, air speed (1～4) * 10
4h
-1, 100 milliliters of catalyst loading amounts, 180～280 ℃ of reaction gas inlet temperatures, conversion ratio 〉=98%.
Embodiment 4
Take by weighing 500 gram natural mordenite zeolites and be dipped in 700 grams and contain boiling reflux 2 hours in the aqueous solution of 70 gram potassium chloride, emit mother liquor, add the aqueous solution that 600 grams contain 60 gram potassium chloride again and refluxed 2 hours, emit mother liquor, be washed to no Cl
-Ion, 120 ℃ oven dry is stand-by down.
Draw platinum ammonia solution 10ml(and contain pt/10mg/ml) be diluted to 350ml with the distillation washing, be added on the above-mentioned potassium type natural mordenite zeolite carrier, left standstill 2 hours, heat evaporate to dryness and in 500 ℃ of air atmosphere, activate 4 hours.This catalyst is for the deep oxidation reaction of toluene, catalyst loading amount 100ml, air speed 15000h
-1, concentration 3000～6000mg/m
3, 170 ℃ of gas access temperature, conversion ratio 〉=99%.
Embodiment 5
Press embodiment 4 described methods, replace Klorvess Liquid to obtain the catalyst of the carrier loaded platinum of calcium type with calcium chloride, activity is also very high, as, to ethanol, the reaction of acetic acid, catalyst-assembly 100ml, reactant concentration 3000～6000mg/ml, air speed 20000h
-1, 180 ℃ of reaction gas inlet temperature, conversion ratio 〉=98%.
Catalysts and its preparation method of the present invention is not limited to the foregoing description.
The advantages such as catalyst of the present invention is compared with the catalyst of existing similar application, and it is low, active high to have a platinum containing amount, and reaction temperature is low, and air speed adaptability scope is big, and is antitoxin, and heat resistance is good, and preparation technology is simple.
Claims (5)
1, a kind of is carrier with the modified natural modenite, and noble metal platinum is the catalyst of active component, it is characterized in that, modified zeolite is a kind of in potassium type, sodium type, the calcium type modenite, and the active component platinum content is 0.02～0.03% of a vehicle weight.
2, the described Preparation of catalysts method of claim 1 the steps include:
A. platinum is fused to chloroazotic acid, and adding concentrated ammonia liquor, to change the platinum ammoniacal liquor into standby;
B. the natural mordenite zeolite modification becomes sodium type, potassium type, ca-form zeolite carrier;
C, modified support is dipped in the platinum ammoniacal liquor exchange absorption platinum, the temperature of modified support exchange absorption platinum is 95～100 ℃, 4～5 hours time;
Product after D, the exchange absorption together with the mother liquor evaporate to dryness after, be raised to 250 ℃ by room temperature, be incubated 1 hour, be raised to again 450～500 ℃ in air atmosphere insulation activated in 4-5 hour.
3, preparation method according to claim 2, it is characterized in that the natural mordenite zeolite modification, by natural zeolite being added in the solution of one of sodium chloride, potassium chloride, calcium chloride, heating is boiled and was realized that the solid-to-liquid ratio of zeolite and solution was 1: the 1.2-2(volume ratio) in 4-5 hour.
4, preparation method according to claim 2, it is characterized in that modified support is dipped in the platinum ammoniacal liquor exchange absorption platinum after, add the reduction of reducing agent formalin, washing again, drying, activation.
5, the described catalyst of claim 1 is used for organic waste-gas purification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100268 CN1020150C (en) | 1988-01-19 | 1988-01-19 | Platinum/zeolite organic waste gas purifying catalyst and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100268 CN1020150C (en) | 1988-01-19 | 1988-01-19 | Platinum/zeolite organic waste gas purifying catalyst and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034319A CN1034319A (en) | 1989-08-02 |
| CN1020150C true CN1020150C (en) | 1993-03-24 |
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ID=4831274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100268 Expired - Fee Related CN1020150C (en) | 1988-01-19 | 1988-01-19 | Platinum/zeolite organic waste gas purifying catalyst and preparing process thereof |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004167306A (en) * | 2002-11-18 | 2004-06-17 | Ict:Kk | Exhaust gas cleaning catalyst and exhaust gas cleaning method |
| CN104525215B (en) * | 2014-11-29 | 2016-07-13 | 北京工业大学 | A kind of preparation method and application of alpha-oxidation manganese nickel-loaded Mg catalyst |
| CN106861748A (en) * | 2017-01-22 | 2017-06-20 | 南昌大学 | A kind of preparation method of multi-stage porous modenite supporting Pt catalyst for catalytic combustion |
| CN112408417B (en) * | 2019-08-22 | 2022-07-01 | 中国科学院大连化学物理研究所 | Modified mordenite molecular sieve and preparation method thereof |
-
1988
- 1988-01-19 CN CN 88100268 patent/CN1020150C/en not_active Expired - Fee Related
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| CN1034319A (en) | 1989-08-02 |
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