Abstract:
A method for the uniform coating of honeycomb bodies with finely divided solid matter from a dispersion in an amount which is below that which arises during customary immersion. To this end, the honeycomb is flooded from below with dispersion, emptied after a dwell time and blown out. Filling time, filling amount, dwell time emptying time as well as the time between emptying and blowing out are measured in such a manner that in order to increase the separated amount of solid matter, filling time, dwell time, pumping-out time and the time between emptying and blowing out are increased but the filling amount is reduced.

Description:
INTRODUCTION AND BACKGROUND 
     The present invention relates to a method for the uniform coating of a honeycomb body formed of ceramic or metal with an amount of the solid matter of a coating dispersion which amount, at a given constant density of the coating dispersion, is below that which arises under equilibrium conditions between the honeycomb body and the coating dispersion. 
     Up to the present invention, when coating porous ceramic carriers of the monolithic type with finely divided oxides, e.g. catalytically active Al 2  O 3  for increasing the surface of a subsequently applied catalytically active component, the carriers were immersed in an aqueous dispersion of the oxide until the complete filling up of the cells occurred or the carriers were flooded with the dispersion. Then, the excess dispersion remaining in the cells was conventionally removed by blowing it out or by removing it by suction (Ullmanns Encyclopedia of Industrial Chemistry, 3d German edition, vol. 9 (1957), pp. 273, 274). Coatings were always created thereby in accordance with the complete saturation of the water-pore volume of the particular ceramic carrier. The known method only permits the use of relatively low-concentrated, that is, highly fluid oxide dispersions, so that multiple coatings with intermediate drying is required in order to apply an amount of oxide which is suitable for the intended purpose The amount of oxide absorbed in the individual instance per carrier is strictly related to the porosity and the absorption capacity of the carrier, so that in many carriers the resulting amounts of oxide loading vary sharply. In addition, the immersion process must be carried out so slowly that no flooding of the front surface on top occurs during immersion and with resulting inclusion of air in the monolithic honeycomb body before the rising liquid column of the dispersion reaches this front surface. If this slow process is not used, uncoated areas remain in the monolithic honeycomb body. 
     A technically rather expensive method described in DE-AS 25 46 489 circumvents the problem of a simple immersion of a monolithic honeycomb body by means of introducing the honeycomb body into a pressure chamber, evacuating this chamber and the honeycomb body located in it including its pores, flooding the chamber with the dispersion and building up an excess pressure in the chamber in order to force the dispersion into the pores as well as subsequently removing the excess dispersion remaining in the cells of the monolithic honeycomb body. This publication does not contain a teaching for a uniform application of desired amounts of solid matter. 
     An object of the invention is to overcome these disadvantages and create a coating method with which a desired amount of coating can be applied in a uniform distribution, independent of a given absorption capacity of a porous ceramic carrier or of a given adsorption action of a metallic carrier, and the scattering of the charged amounts of the coating within a carrier series can be reduced. 
     SUMMARY OF THE INVENTION 
     In achieving the above as well as other objects, a feature of the invention resides in a method for the uniform coating of a honeycomb body formed of ceramic or metal with an amount of the solid matter of a coating dispersion which amount, at a given constant density of the coating dispersion, is below that which arises under equilibrium conditions between the honeycomb body and the coating dispersion. The method of the invention is characterized in that the honeycomb body is introduced into a vertical immersion chamber with the same shape and provided in the interior with at least one inflatable seal. After the sealed condition is produced, the dispersion is pumped into the immersion chamber from below. Then the dispersion is pumped out again after a dwell time and the honeycomb body freed, after loosening of the seal. The honeycomb is removed from the immersion chamber and is freed of excess dispersion by means of blowing it out or removing it by suction. 
     In the process of the invention, the filling time, the filling amount, the dwell time in a flooded state and the pumping-out speed, as well as the time between pumping out and blowing out or removing by suction, are measured in such a manner in accordance with the amount of solid matter to be absorbed, that in order to raise the amount of solid matter, the filling time, the dwell time, the pumping-out time and the time between pumping out and blowing out or removing by suction are increased but the filling amount is reduced. These above described measures can be carried out individually or in any combination. 
    
    
     BRIEF DESCRIPTION OF DRAWINGS 
     The invention is explained further in the following detailed description with reference made to the drawings and to several embodiments. 
     FIGS. 1a and 1b are plots of data showing the distribution of solid matter: 
     FIG. 1a) at the slow filling rate which was previously conventional and 
     FIG. 1b) at a rapid filling in accordance with the present invention. 
     FIG. 2 is a cross-section of the apparatus used for carrying out the present invention. 
     FIG. 3 is a plot of data showing the longitudinal distribution of the wash coat which was achieved in Example 1. 
     FIG. 4 is a schematic cross-section of a portion of a honeycomb showing the radial distribution of wash coat achieved in Example 2. 
     FIG. 5 is a partial perspective view of a section of a honeycomb showing the surface distribution of the wash coat achieved in Example 3. 
     FIG. 6 is a plot of data showing the longitudinal distribution of wash coat achieved in Example 4. 
     FIG. 7 is a presentation of data showing the average values of the absorption of wash coat obtainable in Example 5 using the previous method of operation with a rather large number of honeycomb bodies. 
     FIG. 8 is a presentation of data showing the average values of the distribution of wash coat obtainable in Example 5 using the method of operation of the invention with a rather large number of honeycomb bodies. 
    
    
     DETAILED DESCRIPTION OF INVENTION 
     The following provides additional details of the invention. 
     There are possibilities of controlling the absorption of the amounts of solid matter via the following variables during the course of coating 
     a) Filling speed/filling time 
     b) Filling amount 
     c) Dwell time 
     d) Emptying (speed and time) 
     e) Time between pumping out and blowing out. 
     The individual parameters exhibit different influencing variables thereby: 
     a) Filling speed and filling time 
     The distribution of the solid amount becomes poor in the direction of the channels of the honeycomb at very low filling speeds, that is, very long filling times. An oblique distribution is created with increasing solid-matter concentration from the inflow side to the exit side. This is traced to the fact that the inflowing dispersion generates a rinsing effect in the lower range which decreases upwards with simultaneous concentration of the dispersion. It is therefore important that the honeycomb body is rapidly filled so that the suction action begins practically simultaneously over the entire channel surface. 
     When coating different carrier sizes, the pump output and the opening of the filling flap are to be adapted correspondingly. It was found that a filling time of 4-5 seconds for a part that is 152.4 mm in length is advantageous. 
     b) Filling amount 
     The filling amount can be regulated via the filling time and the measurement of the charge level. Of the two, the measurement of the charge level is the better method since the same amount of dispersion is pumped essentially always into the honeycomb to be coated. It is best to arrange the immersion chamber in such a manner that the upper front surface of the honeycomb always rests at the same height in the chamber and is flooded over at the same height. 
     It turned out that unequal solid-matter charges occur when pumping different amounts of dispersion (expressed via the filling time) through honeycombs of the same size. This is documented by the following Test 1. 
     Test 1: 
     6 monolithic carriers from one and the same manufacturing batch consisting of cordierite with the dimensions: 
     
         ______________________________________144.8 × 81.3 × 127 mm            62 channels/cm.sup.20.2 mm wall thickness______________________________________ 
    
     were coated with increasing filling times with a γ-Al 2  O 3  dispersion and the solid absorption determined. The coating took place under the following conditions: 
     
         ______________________________________δ-Al.sub.2 O.sub.3 dispersion:Density         1.568 kg/dm.sup.3Visc.           40-42 cpTemp.           22.5° C.Dwell time:     0.5 sec.Evacuation time:           8.0 sec.End of evacuation to           4.0 sec.start of blowing out:Duration of coating cycle:           20.0 sec.Blowing-out pressure:           150, 140, 130 mbar/temp. 45° C.______________________________________ weight   BD after    wet            dry         solidCarrier blowing  absorp- dry    absorp-                               filling                                     matterweight out      tion    weight tion  time  absorbedg     g        g       g      g     sec.  %______________________________________569   952      383     754    185   6.7   48.30569   954      385     755    186   6.7   48.31541   916      375     721    180   7.7   48.00544   913      369     721    177   7.7   47.97543   882      339     703    160   8.7   47.20543   878      335     701    158   8.7   47.16______________________________________ 
    
     As the table shows, the absorption of solid matter decreases with an increase in the filling amounts (expressed by a lengthening of the filling time at the same pump output) and the ratio between solid matter absorbed and water absorbed shifts in favor of the water. 
     Dwell time 
     The dwell time is the time between the end of the filling and the start of the pumping out operation. During this time, the honeycomb body stands full of coating dispersion and draws in more water out of the dispersion. The layer located directly on the honeycomb channel wall receives a high concentration of solid matter as a result thereof. 
     As the absorption capacity of the material of the honeycomb body decreases, the influence of the dwell time also drops. The latter is therefore to be adjusted to the composition of the honeycomb body and to the thicknesses of the channel walls. 
     Test 2: 
     Carriers and other parameters correspond to Test 1 (filling time: 6.7 sec.) 
     
         ______________________________________ weight   BD after    wet           BD dry       solidCarrier blowing  absorp- dry   absorp-                               holding                                     matterweight out      tion    weight                        tion   time  absorbedg     g        g       g     g      sec.  %______________________________________550   940      390     735   185    0.5   47.44550   942      392     736   186    0.5   47.45550   955      405     742   192    1.0   47.41550   957      407     743   193    1.0   47.42550   970      420     748   198    2.0   47.14550   967      417     747   197    2.0   47.24______________________________________ 
    
     The solid-matter/water system absorbed by the honeycomb body is shifted in favor of the water by the lengthening of the dwell time. However, wet absorption and dry absorption increase noticeably. 
     d) Pumping out (speed and time) 
     The emptying of the honeycomb bodies by means of the pumping out step after the dwell time has elapsed also influences the amount of wash coat absorbed. It is a function of the pump capacity and the pumping time. 
     The pumping-out time was increased gradually in the following test, which is associated with an improved emptying of the channels of the honeycomb. The absorption ability, which was still present, fixed the deposited coating better onto the channel walls of the honeycomb body. 
     Test 3: 
     Setting and carriers as in Test 1 (filling time 6.7 sec.) 
     
         ______________________________________ weight   BD            BD after    wet           dry   pumping                                     solidCarrier blowing  absorp- dry   absorp-                              out    matterweight out      tion    weight                        tion  time   absorbedg     g        g       g     g     sec.   %______________________________________573   956      383     753   180   8.0    47.00573   959      386     744   171   8.0    44.30557   937      380     738   181   9.0    47.63558   950      392     744   186   9.0    47.45573   968      395     701   188   10.0   47.60575   990      415     775   200   10.0   48.19______________________________________ 
    
     e) Time between pumping out and blowing out 
     The time between the pumping out and the subsequent blowing free or freeing by means of suction likewise affects the absorption of solid matter. This is all the more so when the preceding steps are carried out very rapidly and when there is a distinct short fall in reaching the saturation by means of water absorption. 
     The influence was investigated in Test 4: Carriers and setting as in Test 1 (filling time 6.7 sec.) 
     
         ______________________________________ weight   BD after    wet           BD dry       solidCarrier blowing  absorp- dry   absorp-                               pause matterweight out      tion    weight                        tion   time  absorbedg     g        g       g     g      sec.  %______________________________________570   953      383     753   183    4.0   47.78572   956      384     756   184    4.0   47.92573   952      379     755   182    4.0   48.02573   963      390     760   187    6.0   47.92574   966      392     762   188    6.0   47.98572   957      385     757   185    6.0   48.03571   968      397     762   191    8.0   48.10570   965      395     760   190    8.0   48.09568   967      399     760   192    8.0   48.08______________________________________ 
    
     The amount of dispersion still in the channels after the pumping out operation also exerts an influence. This influence is a function of the pumping-out time and of the installed pump capacity (in Test 4 the emptying pump had a theoretical capacity of 3 m 3  /h). 
     FIGS. 1a and 1b show plots of the distribution of solid matter on a carrier when a slow filling rate is used (Q=1 m 3  per hour; FIG. 1a) and when the rapid filling rate is used in accordance with the invention (Q=3 m 3  per hour; FIG. 1b). In each of the tests in FIGS. 1a and 1b, an alumina wash coat (Al 2  O 3 ) was applied to a carrier having a diameter of 101.6 mm, a length of 152.4 mm, a cell density of 46 cells/cm 2 , and a wall thickness of 0.32 mm. 
     The immersion chamber used in the coating method of the present invention exhibits the following design according to FIG. 2: 
     A rectangular, vertically standing immersion-chamber housing 16 is connected to a rectangular base plate 15 with slightly greater dimensions than the cross section of the immersion-chamber housing. The base plate has a central bore 151 into which a slide bushing 19 is screwed which is protected by bellows 18. The bushing is adapted to receive a plunger 3 which can travel up and down. In addition, filling and emptying line 9 is connected to and passes through the base plate. The plunger shaft carries a support plate 2 for the honeycomb body on its upper end. A rectangular inner housing 11 with an inwardly projecting, upper annular edge is inserted flush into the housing and forms the so-called permanent lower immersion-chamber insert. It defines the drain space 10. 
     A plurality of replacement inserts 12, 13, 14 can be placed on inner housing 11 which designed as an insert. The inserts have the form of disks with a slightly greater opening width than the diameter of honeycomb body 1 (shown in position) so that they quasi form the interior cylinder wall for the reciprocating honeycomb body. The disk thickness and the number of replacement inserts depend on the length of the particular honeycomb bodies to be coated. The lower and upper sections of a given honeycomb body are fixed by inflatable rubber sleeves 7,8 inserted into immersion-chamber housing 16. The outer sleeve form corresponds to the immersion-chamber and the inner sleeve form corresponds to the carrier form. A spring washer 6 resting on replacement insert 13 is inserted underneath rubber sleeve 8 as a support piece for the honeycomb body. An annular fitting 5 arranged above the sleeve functions as the immersion-chamber head 5. 
     Immersion-chamber housing 16 is suspended by conventional support means at 17 on a carrier frame. Bellows 18 protects the slide connection plunger 3 / slide bushing 19 from penetration by the coating suspension. 
     A central light chamber 20 located above the honeycomb body outside of the immersion-chamber head serves to measure the level of filling. The lower position of the plunger is denoted by line 22, the upper position by line 21. The line 23 indicates a possible filling level of the immersion-chamber. 
     The functional operation of the immersion-chamber is as follows: 
     Plunger 3 travels to the upper position 21. 
     Carrier 1 is placed on receiving plate 2 of the plunger. 
     Plunger 3 travels to the lower position 22. 
     Carrier remains standing on support piece 6. 
     Upper sleeve 7 and lower sleeve 8 are inflated. 
     Supply of dispersion via line 9 begins with full capacity of the filling pump or with full opening of the filling valve. 
     Filling time 1 expires. 
     Dispersion supply 9 is operated further with choked output 
     Filling time 2 expires. 
     Light chamber 20 cuts off supply upon attainment of level of filling 23. 
     Dwell time expires. 
     Lower sleeve 8 and upper sleeve 7 are deflated and emptying pump starts up. 
     Emptying time 1 expires. 
     Lower sleeve 8 is inflated. 
     Emptying time 2 expires. 
     Lower sleeve 8 is deflated; 
     Upper sleeve 7 is inflated. 
     Plunger 3 travels upward and pushes honeycomb body 1 by means of receiving plate 2 through the upper sleeve (the adhering wash coat is wiped off thereby on the carrier jacket). 
     Plunger 3 reaches upper position 21. 
     Upper sleeve 7 is deflated. 
     Emptying pump is disengaged. 
     Carrier part is removed and blown out or removal by suction performed. 
     EXAMPLE 1 
     A ceramic carrier body of cordierite (Corning Glass company) with the dimensions: 
     
         ______________________________________Diameter:           101.6 mmLength:             152.4 mmCell density:       42 cells per cm.sup.2Wall thickness:     0.31 mm______________________________________ 
    
     was coated with wash coat in a single stage in the immersion-chamber. 
     The wash coat exhibited the following properties: 
     
         ______________________________________Concentration:     48.7% by weight oxides     (oxide composition: 84.92% by weight Al.sub.2 O.sub.3,     5.30% by weight CeO.sub.2, 6.82% by weight ZrO.sub.2,     2.96% by weight Fe.sub.2 O.sub.3)Viscosity:     50 cpTemp.:    30° C.Particle size:     0 4-5 μm.______________________________________ 
    
     Setting of the immersion-chamber: 
     
         ______________________________________Filling time 1:1.5 sec.                  Filling-flap position 100%                   4.8 sec.Filling time 2:3.3 sec.                  Filling-flap position 20%Dwell time:             0.0 sec.Emptying time 1:        1.5 sec.Emptying time 2:        2.5 sec.Ejection:               0.8 sec.Sleeve pressure above (7):                   2.0 barsSleeve pressure below (8):                   4.0 barsTime until blowing out:                   2.5 sec.Blowing-out pressure:  150 mbarsBlowing-out time:       13 sec.______________________________________ 
    
     The coated carrier part was dried 0.5 h with a 150° C. air current and then tempered 1 h at 500° C. 
     The carrier part had a deposit of 150 g wash coat after tempering. The longitudinal distribution is shown in FIG. 3. 
     EXAMPLE 2 
     A metallic carrier (Behr company) with the dimensions: 
     
         ______________________________________Diameter:           90.0 mmLength:             74.5 mmCell density:       62 cells per cm.sup.2Wall thickness:     0.05 mm______________________________________ 
    
     was coated with wash coat in a single stage in the immersion-chamber. 
     The wash coat used exhibited the following properties: 
     
         ______________________________________Concentration:     56.3% by weight oxides     (oxide composition: 77% by weight Al.sub.2 O.sub.3, 13     % by weight CeO.sub.2, 7% by weight ZrO.sub.2, 3% by     weight Fe.sub.2 O.sub.3)______________________________________ 
    
     Setting of the immersion-chamber: 
     
         ______________________________________Filling time 1:              1.8 sec.Filling time 2:              1.2 sec.Dwell time:                  0.0 sec. Emptying time 1                        4.0 sec.*Emptying time 2Ejection:                    0.6 sec.Sleeve pressure above (7):   4.0 barsSleeve pressure below (8):   4.0 barsTime until blowing out:      1.5 sec.Blowing-out pressure:       100 mbarsBlowing-out time:            8 sec.______________________________________ *A wiping off of the wash coat from the jacket is not necessary in the case of these parts. The sleeve control has been modified in relation to Example 1. After expiration of the dwell time, both sleeves remain closed and open simultaneously with the start of the ejection. 
    
     The coated part was dried standing in an air current 0.5 h in a belt drier at 150° C. and then tempered 0.33 h at 300° C. 
     The absorption of wash coat, determined after tempering, was 82 g. 
     The carrier part was coated very cleanly as determined optically. A determination of the wash-coat distribution took place only in a radial direction according to the drawings, FIG. 4. 
     Coating result in % in the total charge: 
     K 1=101.4% 
     K 2=99.6% 
     K 3=99.9% 
     K 4=100.3%. 
     The equipartition in a radial direction is very good. 
     EXAMPLE 3 
     A ceramic carrier body of mullite (NGK company) with the dimensions: 
     
         ______________________________________Length:             150 mmWidth:              150 mmHeight:             150 mmCell density:       8 cells per cm.sup.2Wall thickness:     0.62 mm______________________________________ 
    
     was coated with wash coat in a single stage in the immersion-chamber. 
     The wash coat exhibited the following properties: 
     
         ______________________________________Concentration:     64.2% by weight oxides     (87% by weight Al.sub.2 O.sub.3, 6% by weight CeO.sub.2, 7%     by weight ZrO.sub.2)Viscosity:     &gt;100 cpTemp.:    30° C.Particle size:     0 8 μm.______________________________________ 
    
     Setting of the immersion-chamber: 
     
         ______________________________________Filling time 1:              4 sec.Filling time 2:              6 sec.Dwell time:                  0.5 sec. Emptying time 1              1.5 sec.Emptying time 2              8.0 sec.Ejection:                    0.7 sec.Sleeve pressure above (7):   0.8 barSleeve pressure below (8):   1.5 barsTime until blowing out:      3.0 sec.Blowing-out pressure:       150 mbarsBlowing-out time:            14 sec.______________________________________ 
    
     The coated part was dried standing in an air current 1 h in a belt drier at 180° C. and then tempered 0.5 h at 240° C. 
     The absorption of wash coat, determined after tempering, was 402 g. 
     The distribution of wash coat can be seen in FIG. 5; it is very uniform in all directions. 
     Surfaces measured on core 1-core 4 (in m 2  /g): 
     
         ______________________________________Core 1       Core 2  Core 3     Core 4______________________________________a     16         16      16       16 upper thirdb     16         17      16       17 middle thirdc     17         16      17       16 lower third______________________________________ 
    
     EXAMPLE 4 
     A ceramic carrier body of cordierite (Corning Glass company) with the dimensions: 
     
         ______________________________________Length:             160 mmWidth:              169.7 mmHeight:             80.8 mmCell density:       62 cells per cm.sup.2Wall thickness:     0.16 mm______________________________________ 
    
     was coated with wash coat in a single stage in the immersion-chamber. 
     The wash coat exhibited the following properties: 
     
         ______________________________________Concentration:       58.05% by weight oxides       (oxide composition: 72% by weight Al.sub.2 O.sub.3,       26% by weight CeO.sub.2, 2% by weight ZrO.sub.2)______________________________________ 
    
     Setting of the immersion-chamber: 
     
         ______________________________________Filling time 1:       2.5 sec.Filling time 2:       3.0 sec.Dwell time:           0.0 sec. Emptying time 1       2.0 sec.Emptying time 2       2.0 sec.Ejection:             0.6 sec.Sleeve pressure above (7):                 1.0 barSleeve pressure below (8):                 3.0 barsTime until removal    2.5 sec.by suction:Suction vacuum:      400 mbars (negative pressure)Suction time 1:       7.0 sec.Pause time:           3.0 sec.Suction time 2:       9.5 sec.______________________________________ 
    
     The carrier part treated by suction was dried by standing in an air current 0.5 h in a belt drier at 150° C. and then tempered 1 h at 500° C. 
     The absorption of wash coat, determined on the tempered part, was 296 g. 
     The distribution of wash coat in the longitudinal direction is shown in FIG. 6. 
     EXAMPLE 5 
     A process comparison with a rather large number of ceramic carrier bodies of the Corning Glass company was carried out: 
     
         ______________________________________Diameter:            101.6 mmLength:              152.4 mmCell density:        42 cells/cm.sup.2Wall thickness:      0.31 mm.______________________________________ 
    
     The oxide coating applied had the following composition: 
     
         ______________________________________   Al.sub.2 O.sub.3         86.0%   CeO.sub.2 :         6.3%   ZrO.sub.2 :         5.4%   Fe.sub.2 O.sub.3 :         2.3%______________________________________ 
    
     Nominally, 154±23 g of wash coat should be deposited per carrier part. 
     
         ______________________________________                        according to the             traditional                        inventionAmounts and conditions:             FIG. 7     FIG. 8______________________________________N =               2,600 pieces                        2,600 piecesn =               104 pieces 104 piecesConc. g % =       42.2-43.8  46.76-47.17Viscosity cp =    38-42      49-55No. of immersion steps =             2          1Charge size:      100 piecesSpecimens per charge =             5 pieces______________________________________ 
    
     FIGS. 7 and 8, show data relating to the average value of the absorption of the wash coat (X(g)) from Example 5, and the scatter of the individual values (R(g)). FIG. 7 shows this data for a previous method of operation, and FIG. 8 shows this data for the method in accordance with the invention. 
     In the case of the traditional amounts and conditions, the production was characterized by sharp fluctuations of the average value of the absorption and also by scatterings of the individual values which scatterings were just as great: 
     Process capacity=cp value&lt;1.0. 
     In the case of the coating process in accordance with the invention, a uniform course of the average value with low scatter resulted: 
     Good process capacity=cp value&gt;2.0. 
     cp value 
     The cp performance index represents a relation between the process performance and the specification tolerances. 
     
         ______________________________________ ##STR1## ##STR2##σ = standard deviationcp value    interpretation______________________________________&lt;1.00       poor, process necessarily also produces       rejected material1.00-1.33   barely acceptable1.34-2.00   good, justifies continues attempts at       improvement&gt;2.00       excellent, goal to be striven for on a       long-term basis______________________________________ 
    
     Further variations and modifications of the foregoing will be apparent to those skilled in the art and are intended to be encompassed by the claims appended hereto 
     German priority applications P 40 06 205.8 and P 40 40 150.2 are relied on and incorporated by reference.