前苏联专利SU1530083A3 Method of removing soot from exhaust gases of diesel engines

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专利摘要:
Ein Verfahren zur Herabsetzung der Zündtemperatur von aus Dieselmotorabgas abgefiltertem Dieselruß benutzt als katalytisch aktive Substanz, über die das Abgas geleitet wird, Lithiumoxid, Kupferchlorid, Vanadinoxid/Alkalimetalloxid-Kombinationen, Lithium-, Natrium-, Kalium- oder Cervanadat oder ein Perrhenat, vorzugsweise des Kaliums oder Silbers oder mehrere dieser Substanzen.
公开号:SU1530083A3
申请号:SU833595950
申请日:1983-05-20
公开日:1989-12-15
发明作者:Домесле Райнер；Коберштайн Эдгар；Плетка Ханс-Дитер；Фелькер Херберт
申请人:Дегусса Аг (Фирма)；
IPC主号:

专利说明:

This invention relates to methods for diesel soot from diesel engine exhaust gases.
The purpose of the invention is to reduce the ignition temperature of diesel soot.
Figure 1 shows the filter housing, a horizontal projection; figure 2 section of the diesel filter in the form
a monolithic structural hardener of catalyst from cordierite with porous walls of flow channels, in which the channels are blocked from the inlet and outlet streams by a ceramic plug (these plugs are distributed in such a way that, if necessary, an open channel stands against the locked end of the channel).

O4
The catalytically active substance can be applied to the carrier substance or mixed with it. Alumina, silicon dioxide, titanium dioxide, zirconium oxide and rare-earth metal oxides, as well as copper chromite, nickel and iron oxides are used as carrier materials. The filter can be made in the form of a packing of metallic or mineral fibers coated with catalytically active materials. substances or mixed with these substances.
The catalytically active substance is contained in an amount of 4 g / m of the geometric surface of the filter element. 10-100, preferably 20-CO g / m can be applied to a monolithic filtering body of cordierite with a diameter of 11.85 cm long of 15.25 cm and 15.5 cells / cm.
Since diesel soot consists not only of carbon particles, but also contains up to 20-30% of adsorbed volatile hydrocarbon, it may be beneficial to apply a platinum-group noble metal catalyst on the inlet side, sometimes in combination with a metal oxide, for example f , The carbon monoxide formed during the combustion of diesel soot is converted on the catalyst from a noble metal to harmless carbon dioxide,
PRI me R 1. 20 g of LiOH and 75 g of oxalic acid are dissolved in 500 deionized water. The resulting solution of lithium oxalate is applied for impregnation operations with intermediate drying on the filter body of cordierite (Fig. 1) with a diameter of 11.85, a length of 15.25 cm and containing 15.6 cells / cm. After the final drying at 110 ° C, lithium oxalate is decomposed to form at the expense of two-step aging at 600 ° C.
Example2. 100 g of CuCl are milled with YO ml of deionized water in a ball mill for 2k hours. Then the solution is filled up with deionized water to a volume of ml and half of this volume (280 ml) is filled in with a filter as in example 1, from the end, then A h is dried in the cabinet at 100 ° C. The absorption of CuCl reaches 50 g.
Example 25 g and 6.6 g Li01 are dissolved in a beaker
ml
two
e 1530083l
in 250 ml of deionized water when heated. This solution is impregnated with the filter housing as in Example 1. It is then dried at and 2 hours at 700 ° C to form lithium metavanadate.
e r. 40 g of NaVC, solution P p and
250 ml of deionized water with stirring. The sodium vanadate solution is spilled from the front side through the filter housing of example 1, while sucking the entire amount of the solution. Subsequent drying is carried out at 150 ° C.
PRI me R 5. Prepare a solution of tO g KVOj in 50 ml of deionized water. With this solution in Example 1, the filter housing is impregnated twice on the butt side with an intermediate 2-hour drying at 250 C. Final drying after 2 hours also results in a finished catalytic filter.
Example 100 g of (NH4) 2C1 (NO,) are dissolved in 1 L of deionized water and 200 ml of concentrated nitric acid. 28 g of NaVC--, dissolved in 500 ml of hot water, are added and the mixture is heated to 80-100 s. The precipitated cerium vanadate (iv) (2Se02 V Oj pN O) is washed repeatedly with warm water and freed from nitrates, then mixed with AOO ml of a ball mill overnight. The ground mass is poured with water to 550 ml and this mixture is covered with one side of a diesel filter in example 1, and the excess suspension is blown out. After 3 hours of drying at 300 ° C, the action is repeated on the same side of the filter. Absorption of cerium vanadate (iv) reaches 30 g.
Example7. Og is placed in a beaker with 600 ml of deionized water and stirred for 15 minutes. The filter housing of example 1 is poured from the front side of the suspension thus obtained, and the excess suspension is blown out with air. After drying
for 1.5 hours, the impregnation is repeated. Finally, drying is carried out for 5 hours at 120 C. Now the filter is covered on one side with approximately 37 g of V ,. Then the filter is poured with the same
side 250 ml 0, KOH solution. After one hour of drying during and heat treatment for the same time in a muffle furnace with
coated catalytic filter ready for operation. The catalyst consists of admixture with 1.1 wt.%.
PRI me R 8. A filter is prepared similarly to example 7, but using a KOH concentration. The catalyst consists of VjOg mixed with H, wt.%.
Example 9 South of sodium oxalate is dissolved in a 250 ml solution of vanadium (iv) oxalate VOCjO. The resulting solution is impregnated with the filter housing of Example 1. After drying at 150 ° C, they are kept for 3 hours at ZVO ° C to decompose the starting compounds to and. Prepared with admixture of 1b, 8 masd.
Example 10. 50 g of a mixture of copper chromite and G-alumina (75 and 25 wt.h.), k g NiO, 10 g of TiOj and 50 g (the latter with an admixture of 3 wt. KO) is ground in a ball mill , 5 ml of concentrated nitric acid and tOO ml of deionized water for 2 ° C. Then the ground mass is diluted with deionized water. 1530083
Example 12. 30 g KVOj and 5 g
The KB.eO is dissolved in 500 ml of deionized water and the solution is divided into two
equal parts by volume. The monolithic filter housing, as in Example 1, is first doused with the first half of the solution by drenching. After intermediate drying with the same
1Q the second half of the solution is applied to the filter housing. Following the new drying at 250 ° C, aging at 450 ° C is carried out. The catalyst contains, by weight: KVO, 85.71; KReO,
15 .
PRI me R 13. A filter case coated with CuCl, as in Example 2, is impregnated in two operations with a solution of 30 g KVOj and 5 g KRe04 in 500 ml of water.
20 The intermediate and final drying is carried out at 100 C. A catalyst is obtained containing, wt%: KVOj 35, 30; KReO 5.88; CuCl 58.82.
PRI me R I. Diesel filter.
25 analogously to Example 1, from the side of the end, 5 g are coated from 10% dispersion containing noble metals (platinum and palladium) in weight
The total ratio of 2: 1 in the form of yTtCl is up to 1 liter of total volume and similarly to Q and .. Total, together with 45 g of oxide, example 1, the filter is coated with a single aluminum filter and absorbs 2.58 g of an AOO side with this mixture ml. Then, they are dried for 3 hours at 300 ° C. The absorption of solids reaches 45.6 g. The side covered with the mixture is the inlet side for exhaust gases. The catalyst contains, wt%: 2, Kj.0 1.32; copper (II) chromite 32.90; G-A12.05 10.96; Nio .3.51; TiOi, 8.77.
Example 11. In a solution of 1.2 g Cu (N05) 2 per 100 ml of deionized. 50 g of TiO are added to the water and the mixture is dried in an oven for 2 hours. From the obtained product, 25 g are taken and mixed with 25 g, the latter mixed with 3% KjO and 200 ml of deionized water, containing 0.5 g of KOI, for 2 hours in a ball mill. Then it is diluted with water to 280 ml and, similarly to example 1, the diesel filter is covered with a layer of mixture at the end. After drying for 2 hours in a drying oven at 300 ° C, a filter is obtained that is coated with a mixture of mixture on the inlet side for exhaust gases. The composition of the catalyst, wt .:, 25; KjO 0.75; CuO 0.16; TiOi 2k, Qk.
platinum and 1.29 g palladium. After further drying overnight at 250 ° C and thermal decomposition of the base metal compounds at 600 ° C for 2 hours in a muffle furnace, these compounds are reduced for 2 hours at 550 ° C in a stream of hydrogen. A supported catalyst is obtained. ; wt%: Pt 5.28; Pd 2 ,, -Al-Oj the rest. After cooling, the other, not yet coated side of the filter is impregnated as in Example 5 with potassium metavanadate and then used as the inlet side of an exhaust gas filter.
PRI me R 15. A diesel filter, as in example 1, is covered analogously to example AND On the one hand, half of the composition containing the noble metal, and on the other hand, 40 g of VgOj with an admixture of 5 wt.%. The latter is the inlet side for exhaust gas.
f l p and mep 1b. The catalysts made according to examples 1-15 were checked, the filters were installed in the exhaust gas stream of a diesel engine and checked
45
50
55
.

30083
Example 12. 30 g KVOj and 5 g
The KB.eO is dissolved in 500 ml of deionized water and the solution is divided into two
equal parts by volume. The monolithic filter housing, as in Example 1, is first impregnated with drench with the first half of the solution. After intermediate drying with the same
1Q, the second half of the solution is applied to the filter housing. Following the new drying at 250 ° C, aging at 450 ° C is carried out. The catalyst contains, by weight: KVO, 85.71; KReO,
15 .
PRI me R 13. A filter case coated with CuCl, as in Example 2, is impregnated in two operations with a solution of 30 g KVOj and 5 g KRe04 in 500 ml of water.
20 Intermediate and final drying is carried out at 100 C. A catalyst is obtained, containing, in wt.%: KVOj 35, 30; KReO 5.88; CuCl 58.82.
PRI me R I. Diesel filter.
25 analogously to example 1, from the side of the end cover 5 g of a 10% dispersion containing noble metals (platinum and palladium) in weight 5
2: 1 ratio in the form of yTtCl Q and .. Total, together with 45 g of alumina, 2.58 g is absorbed by the filter.
platinum and 1.29 g palladium. After subsequent drying overnight at 250 ° C and thermal decomposition of the base metal compounds at 600 ° C for 2 hours in a muffle furnace, these compounds are reduced for 2 hours at 550 ° C in a stream of hydrogen. A supported catalyst is obtained, containing Q content; wt%: Pt 5.28; Pd 2 ,, -Al-Oj the rest. After cooling, the other, not yet coated side of the filter is impregnated as in Example 5 with potassium metavanadate and then used as the inlet side of an exhaust gas filter.
PRI me R 15. A diesel filter, as in example 1, is covered analogously to example AND On the one hand, half of the composition containing the noble metal, and on the other hand, 40 g of VgOj with an admixture of 5 wt.%. The latter is the inlet side for exhaust gas.
f l p and mep 1b. The catalysts made according to examples 1-15 were checked, the filters were installed in the exhaust gas stream of a diesel engine and checked
five
0
five
functioning to reduce the soot ignition temperature. Used A-cylinder engine with direct fuel injection, diesel. The working volume of the cylinder is 1,6 l, engine capacity is 40 kW. In the soot filter loading phase, the speed was 2900 per minute, load 33 N, oxygen content in exhaust gas IV lA, 2 vol.%. In the soot loading phase, the filter was in the exhaust gas stream until a pressure difference was established on the filter 150. mbar To establish the ignition temperature, the load at a constant number of 2EOO rpm was continuously increased until the differential pressure rose to filter. The temperature attained in the exhaust gas stream before the filter is defined as the ignition temperature, since at a constant differential pressure no further accumulation of soot occurs, which means that a balance is established between the filtered and burned soot.
The table shows the ignition temperatures together with the corresponding load and oxygen content in the exhaust gas when the filter is installed at a distance of 1 m from the engine at 2900 rpm.
As follows from the table, the proposed method achieves a reduction in the ignition temperature of soot by B1-205 ° C compared to using a filter without a catalyst, while in the known method the ignition temperature of soot is reduced only by 50 C.

权利要求:
Claims (2)
[1]
1. A method of removing soot from diesel engine exhaust gases, comprising passing the exhaust gases through a filter with a supported catalyst and burning trapped soot, characterized in that. that in order to lower the temperature
five
0
five
0
five
0
five
0
ignition of diesel soot, use a catalyst consisting of lithium oxide or copper chloride (l), or metavanadate — lithium, sodium, potassium or cerium, or vanadium pentoxide containing an admixture of alkali metal oxide in the amount of 1.1-1b , 8 wt. from the mass of vanadium pentoxide, or from vanadium pentoxide with an admixture of potassium oxide in a mixture with copper (II) chromite, J-alumina, nickel oxide and titanium dioxide with the following content of ingredients, wt .: Vanadium pentoxide, 5 Potassium oxide 1 , 32
Chromite copper (ts) 32,90 U-oxides aluminum 10.9 Nickel oxide 3.51
Titanium dioxide 8,77 or from vanadium pentoxide with potassium oxide impurities mixed with copper oxide (ll) and titanium dioxide with the following content of ingredients, wt .: Vanadium pentoxide, 25 Potassium oxide 0,75
Copper (II) oxide 0.1b Titanium dioxide 2.8 or from potassium metavanadate mixed with potassium perrhenate with the following content of ingredients, wt.%:
Potassium metavanadate 85.71 Potassium perrhenate 1.29 or potassium metavanadate mixed with potassium perrhenate and copper chloride (J) with the following content of ingredients, ma c. %:
Potassium metavanadate 35.30 Potassium perrenate 5.88 Copper chloride (l) 58.82
[2]
2. The method according to claim 1, characterized in that when using a catalyst consisting of potassium metavanadate or vanadium pentoxide mixed with potassium oxide, the gas to be purified is additionally passed through a catalyst consisting of platinum, palladium and y-alumina at the following content of ingredients, wt.%: Platinum 5,28
Palladium2,6
U-Alumina Else
Phie.g

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

DE3232729A|DE3232729C2|1982-09-03|1982-09-03|

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