Journal of Natural Gas Chemistry 14(2005)181188

Influence of Successive Washing on Porous Structure of Pseudoboehmite

Yuefeng Yan, Jianping Zhi , Gaoyong Zhang
State Engineering Center of Surfactant, China Research Institute of Daily Chemical Industry, Taiyuan 030001, China [Manuscript received May 26, 2005; revised August 15, 2005]

Abstract: The effect of successive washing instead of traditional intermittent washing on the porous structure of pseudoboehmite was investigated by mercury porosimetry, N2 adsorption and thermal analysis, while the stabilities of different types of crystals were investigated by X-ray diffractometer. Experimental results show that successive washing is a continuation of the aging process of intermittent washing. After a successive washing, the pore types showed no difference with the intermittent washing. During successive washing, the characteristics of the pores in the range of 215 nm changed only very little. However, the distributions of the pore radius for pores of 2050 and 3001000 nm were obviously influenced. It was shown that the volume of larger pores decreased only to a smaller extent after the successive washing, as compared with that of the intermittent washing, and the pore size was affected by the condition of the successive washing. The roles of physisorbed water, intermicellar liquid, weakly bonded water, as well as the role of stirring, have been discussed. Key words: successive washing, intermittent washing, pseudoboehmite, -Al2 O3 , porous structure

1. Introduction As we know, the structure and performance of -Al2 O3 are determined by the pore structure of its precursor, namely, the pseudoboehmite. Some factors influencing the pore structure of the pseudoboehmite have been reported, and among them the washing process is one of the important factors because: (1) the adsorbing on the surface of the pseudoboehmite acts as a stabilizing factor for amorphous particles [1], and washing can remove the Cl anions, thus enhancing the transformation of the colloidal amorphous particles into the pseudoboehmite; (2) the residual amorphous particles have become smaller after aging, and their solubility in the medium is higher, thus they can be easily removed by washing; (3) the removal of the impurity anions is beneficial for enhancing the stability of the sol formed in the acidification course and hence improve the mechanical strength of the dried granules [2].

Many researchers have emphasized the effect of the washing medium [3] and the additives [4] during the washing stage in the preparation of -Al2 O3 . Intermittent washing is employed in almost all of the Al2 O3 preparations both in manufacturing and laboratory scales. Hou et al. [5] have studied the improvements attained with various washing modes. They introduced countercurrent washing to replace the repeated dispersion mode for the sake of saving water. However, their approach still belonged to the intermittent washing mode. The disadvantages of intermittent washing are as follows: (1) unfavorable yield, (2) larger water consumption, (3) too long manufacturing cycle, (4) low production efficiency, (5) high labor intensity, and (6) large amount of liquid waste. It is possible to solve the above problems if the intermittent washing mode is replaced by the successive washing mode. However, when utilizing the successive washing, it is important to first understand what changes will be brought about to the structure and the

Corresponding author. Tel(0351)4132049; E-mail: zhijianping@ridci.com.cn.

182

Yuefeng Yan et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

performance during the successive washing. Therefore, we have investigated the effects of successive washing on the pore structure of the pseudoboehmite, and the results are reported here. 2. Experimental 2.1. Successive washing technologypar The equipment of washing and the two different washing modes are shown in Figure 1.

pH value, temperature and stirring are important parameters for controlling the solubility equilibrium of the Cl anions.

Figure 2. Flow sheet of intermittent washing

Figure 1. Flow sheet of washing 1BMJ 0.5/310 open delivery washability plate-and-frame type lter press (closed delivery unwashability type), 2LZBF15owrator, 3Pressure gange, 4QFK-100enamel antirot reactor, 5I-1Bscrew pump, 6Stainless steel store tank, 7 Temperature recorder and controller

The procedure of the intermittent washing includes the transportation of the aged stuff, filtering, discharging of the filter cakes and their dispersion in water, and repeating of the procedure for three times (Figure 2). During the intermittent washing,

The successive washing process is different from the intermittent one. As shown in Figure 3, the procedure only includes one filtration and one discharging of the solid stuff. After transporting of the aged stuff by opening valve 1 and filtering, the successive washing is started. By opening water valve and closing stu valve, water will be pumped with an appropriate flux into the pipeline and enter the space between the plate and the filtering cloth, as indicated by the solid line in Figure 3. Then, the exit valve of filter plate 2 (see Figure 3) should be closed. Water will then be pressed through the filtering cloth, the filter cake, and the filtering cloth on the other side, and finally flows out of the filtering equipment (washing plates 1 and 3 in Figure 3). In order to make comparison with the results of intermittent washing, the washing water was stored in an anti-corrosion enamel reactor, and was divided into three successive portions to pass through the washing equipment during successive washing.

Figure 3. Flow sheet of successive washing

2.2. Orthogonal design Preferable technical parameters were obtained by the orthogonal experiment. Levels of factors are shown in Table 1. We used the Table L27 (13 ) [6] to 3

conduct the experiment. A series of samples (nm) were obtained, n=127, denoting the batch number of successive experiment, and m=03, denoting three washing stages. For n=0, the samples were taken from the intermittent washing mode.

Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

183

Table 1. Levels of factors in orthogonal experiment Levels of factors 1 2 3 1 / 40 60 80 First washing stage pH1 9.3 10.3 11.3 V1 /(L/h) 50 100 150 t1 /min 5 10 15 2 / 40 60 80 Second washing stage pH2 9.8 10.6 11.0 V2 /(L/h) 50 100 150 t2 /min 5 10 15 3 / 40 60 80 Third washing stage pH3 10.0 10.6 11.4 V3 /(L/h) 50 100 150 t3 /min 5 10 15

: temperature; V : velocity of ow; t: time of air flow.

2.3. Preparation of samples Parameters of successive washing are shown in Table 2, which are chosen through variance analysis for orthogonal experiment, using mass fraction of Cl in the filter cake as index. After slurrying, the aged stuff were pumped into an open delivery plate-and-frame

type filter press. Then the temperature and pH of deionized water were adjusted according to Table 2 for conducting the three stage washing, and finally the filter cake was discharged. During this course, concentrations of Cl in the filter liquor and the cake were exact determined.

Table 2. Parameters of successive washing process n 7 9 25 27 First washing stage 1 / 40 40 80 80 pH1 11.3 11.3 11.3 11.3 V1 /(L/h) 150 150 100 100 t1 /min 15 15 5 5 2 / 40 80 40 80 Second washing stage pH2 9.8 11.0 11.3 10.6 V2 /(L/h) 50 150 100 50 t2 /min 15 10 15 10 3 / 80 60 60 40 Third washing stage pH3 11.3 10.6 10.0 11.3 V3 /(L/h) 100 50 100 50 t3 /min 10 5 5 15

n: Batch number of the successive washing experiment

2.4. Characterization of samples 2.4.1. X-ray dif fraction determination X-ray diffraction determinations of the pretreated samples were conducted by using a Japanese Rigaku D/max-RB X-ray diffractometer with a K operated at 40 kV, 100 mA, DS=SS=1o , RS=0.3 mm1 , and scan rate 0.25o /min (RC=1s). 2.4.2. N2 adsorption Surface areas, pore volumes, and pore radius of narrow pores were measured by an ASAP2010 instrument made in Japan. Samples were dried at 120 to get rid of adsorbates on the surface before the measurement. BET areas were calculated according to the Brunauer-Emmett Teller equation, and the total pore volumes were obtained with p/p0 =0.99. 2.4.3. Mercury porosimetry measurement Distribution of macropore radius was determined by a Thermoquest Pascal-240 Mecury porosimetry of America manufacture after drying at 120 . 2.4.4. Thermal analysis-TG(DTG) and DTA

DTA and TG data were obtained by a Setaram Tga 92 thermal analysis instrument made in France, with Pt/Pt-10%Rh, and -Al2 O3 as the reference. Heated in argon gas at increments of 10 /min, the weight of the samples decreased gradually. If the temperature was above 600 , the types of the crystals of the samples would be changed, so 650 was chosen as the ultimate temperature in thermal analysis. 3. Results and Discussion 3.1. Change of pore types after successive washing The isotherm plots are shown in Figures 4 and 5. The hysteresis loop shows the presence of medium pores in the samples obtained either by intermittent or successive washing. These medium pores were originated mainly from the interspaces of crystalline particles or their aggregates. The samples 0-0 and 0-1 prepared by intermittent washing consisted of mainly ink-bottle type pores (H2 type or E type), and part of them was cylindrical pores. Similar conclusion can also be obtained from the increasing trend of the t-ns curve. Results of the t-equation after correction are shown in Table 3. The

184

Yuefeng Yan et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

Figure 4. Isotherm plots of intermittent washing

Figure 5. Isotherm plots of successive washing

ink-bottle type pores cannot be easily explained, but different mechanisms in capillary shrinkage and evaporation between the narrow neck and the wide body are possible explanations, that is to say, the pore type

is influenced by the texture of the material. Whatever the reason for forming of the ink-bottle type pores, the adsorption branch should be used for the analysis of the pore distribution.

Table 3. orrected results of t-equation for pore types of the samples Physical-chemical parameters of the samples Specific surface area (m2 /g) Pore volume (p/p0 =0.99) (ml/g) t-Area (m2 /g) Micropore volume (ml/g) Pore volume (ml/g) cylindrical pores slit-shaped pores ink-ottle pores Pore diameter (nm) cylindrical pores adsorption slit-shaped pores desorption ink-ottle pores adsorption Specific surface area (m2 /g) cylindrical pores slit-shaped pores ink-ottle pores Samples 0-0 117.1 0.20 90.39 0.00004 (0.12) 0.20 (3.32) 6.67 (90.1) 117.3 7-3 264.6 0.47 233.7 0.014 0.48 (0.46) 7.1 (2.13) 257.6 (243.0)

From Figure 5, we can conclude that for the samples of 0-2, 0-3 and 7-3, 25-3, 27-3 etc, the pore types mainly consisted of cylindrical pores (H1 type or A type), and part of them was slit-shaped pores (H3 type or B type). The values of specific surface area and the t-ns curve could confirm these results as well, since the value of 257.6 m2 /g is approximated to the BET value of 264.6 m2 /g. Besides, the isotherm plot shows that the pores also have the characteristics of the slit-shaped pores, because adsorption is unlimited when p/p0 is high enough. The size of the mi-

cropore radius is 1.13 nm calculated using the slitshaped pores mode, which is typical of micropores, and this kind of pores constitute the layer structure of the pseudoboehmite. With the increment in the extent of washing, the pore type changed from the ink-bottle shape into the cylindrical shape, because the neck of the pores was shortened and widened. Thus, we can conclude that there is no difference in pore types between the pseudoboehmites prepared by successive washing and intermittent washing.

Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

185

3.2. Ef fect of successive washing on pore radius distribution 3.2.1. Results of thermal analysis DTG curves of the samples 0-0, 0-3, 7-3 and 27-3 with different peaks are shown in Figure 6. It has been reported [6] that the peak at the higher temperature is associated with intermicellar water bonded with the crystal lattice via the OH group, and the lower temperature peak is originated from the loss of water in macropores of the pseudoboehmite, while the peak appearing at the mid-temperature range is resulted from the loss of the water weakly bonded to the crystallites. As shown in Figure 6, there are two peaks in the DTG curve of the samples 7-3 and 27-3,

row pores yielded after successive washing are larger than those formed after intermittent washing, and the pore volume of the former is smaller than the latter. This conclusion can also be obtained from Table 6. In Figure 7, the DTA plots have the same trend as that of the DTG patterns, due to the fact that there was no transformation of the crystal type. The degree of crystallization follows the order of: (27-3)>(27-3) >(7-3)>(25-3)>(3-0). 3.2.2. Ef fect of successive washing on total pore volume The total pore volumes (mm3 /g) obtained by mercury porosimetry are shown in Table 4, and the increment in volume relative to the intermittent washing samples are also given. It can be seen that the two washing modes showed the same trend of alteration, that is, they both increase at first, and then decrease. But the values of the pore volumes are different from each other. Combining with the technical parameters in Table 2, we can derive the following conclusion by making lateral and perpendicular comparisons: lower temperatures and higher pH values are beneficial to the forming of larger pore volumes. The difference in pore volumes is mainly determined by the amount of ammonia present in the wash water, and this is consistent with the results of Ref. [8], which reported that ammonia is an effective pore-enlargement reagent. By compared with the results of intermittent washing, it can be found that the technical parameters of sample 7 are the optimal ones.
Table 4. Total volume of the samples Washing stage (m) 0 1 2 3 0 668.6 1042.9 1041.5 979.5 Total volume of the samples (n) (mm3 /g) 7 668.6 1151.1 1201.8 925.8 25 668.6 942.5 1014.3 761.9 27 668.6 948.4 358.3 528.9

Figure 6. DTG curves

3.2.3. Data of pore structure

Figure 7. DTA curves

where the peak at the higher temperature represents the existing of less structural liquor as well as larger crystallite particles obtained by successive washing. Consequently, we can infer that the radius of the nar-

Distributions of the pore radius of different samples are shown in Figure 8, including the distribution of narrow pores (Figure 8) obtained by N2 adsorption measurement, and the distribution of wide pores (Figure 9) obtained by mercury porosimetry.

186

Yuefeng Yan et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

Figure 8. Distribution of pore with narrow radius

For the sake of comparison, pores are generally divided into three ranges: medium pores of 310 nm, medium pores of 10100 nm and wide pores of 100 1000 nm. The volumes of these three sorts of pores are shown in Table 5. It can be noted that sample 7-2

shows data quite different from the others. General parameters for the porous structure of the samples are shown in Table 6 to serve as references for studying the effect of successive washing on narrow pores and wide pores.

Table 5. Distributions of three sorts of pores Sample 0-0 0-1 0-2 0-3 7-1 7-2 7-3 25-1 25-2 25-3 Volume of 310 nm pores (cm3 /g) 0.09 0.20 0.20 0.17 0.20 0.19 0.17 0.15 0.20 0.11 Percentage of 310 nm pores in all pores (%) 13.5 19.9 19.2 17.3 18.0 15.7 18.1 15.7 19.6 14.2 Volume of 10200 nm pores (cm3 /g) 0.16 0.20 0.17 0.22 0.24 0.51 0.28 0.19 0.20 0.17 Percentage of 10200 nm pores in all pores (%) 24.0 19.9 16.3 20.4 21.6 42.1* 29.8 20.0 19.6 22.1 Volume of 2001000 nm pores (cm3 /g) 0.41 0.65 0.67 0.61 0.71 0.51 0.49 0.61 0.62 0.49 Percentage of 2001000 nm in all pores (%) 61.4 60.2 64.4 62.2 64.0 42.1* 52.1 64.2 60.8 63.6

* Sample 7-2 have a great change, as shown in the Table. Table 6. Parameters of the porous structure of the samples Sample 0-0 0-1 0-2 0-3 7-1 7-2 7-3 25-1 25-2 25-3 27-1 27-2 27-3 R1 /nm 3.34 3.08 4.00 3.98 4.10 3.95 3.55 4.00 4.10 4.20 3.95 3.95 3.85 V1 /(mm3 /g) 200 470 540 510 500 500 470 500 500 480 490 490 480 SP1 /(m2 /g) 117 297 259 251 243 255 265 252 244 229 248 248 249 R2 /nm V2 /(mm3 /g) SP2 /(m2 /g) R3 /nm 786.6 969.9 889.1 868.5 803.6 821.4 889.3 820.9 830.5 770.3 888.9 830.1 911.1 V3 /(mm3 /g) 578.4 896.2 843.4 814.2 948.7 1017.0 914.2 926.0 1023.2 919.8 923.5 987.1 908.2 SP3 /(m2 /g) 0.0008 0.0650 0.0810 0.0750 0.0960 0.0660 0.0750 0.0750 0.1500 0.0730 0.0440 0.0320 0.4400

27.0

10.2

1.0

R1 , R2 , R3 : the main pore radius of 310 nm, 10100 nm and 1001000 nm pores respectively V1 , V2 , V3 : total volume of pores of 310 nm, 10100 nm and 1001000 nm pores respectively SP1 , SP2 , SP3 : specific area of pores of 310 nm, 10100 nm and 1001000 nm pores respectively

Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

187

3.2.4. Ef fect of successive washing on narrow pores 3.2.4.1 Micropores When calculating according to the t-plot equation, only a small amount of micropores (0.0120.017 mm3 /g ) are present in the pseudoboehmite after successive washing. The same conclusion was obtained for intermittent washing. Micropores are controlled by the self-evaporation process in a general sense, so the distribution of micropores would not change very much by the change in the washing mode. 3.2.4.2 Medium pores (310 nm) As has been reported in some references [7], factors influencing the radius of narrow pores include technical conditions of the washing process, such as neutralization, aging, acidification and so on. Transformation of crystal types is the key factor affecting the particle radius and the pore distribution during the aging and washing process. X-ray patterns shown in Figure 10 indicate that there is no difference among the crystal types of the samples, but the degree of crystallization increased more remarkably after the successive washing than the intermittent washing, which resulted in the difference of the distribution of pore radius in Figures 8 and 9. But all in all, the changes are not obvious. 3.2.4.3 Medium pores (1050 nm) In Figure 9, there is a wide peak at 27 nm for the sample 7-2, but it is a reverse of sample 25-2 which was washed at a different pH. This was resulted from the changes in the assembling state of the samples. During continuous mass transfer, the net structure of the gel has come into being. The stablizing factor of the gel is electrostatic force. When pH is higher in the first washing stage, the NH+ ions surrounding 4 the colloid surface will lead to the formation of bridges in the gel, so that the change in assembling state is not obvious. But when the pH is decreased suddenly, hydrophobicity of the colloid surface is weakened as wel, so that the space between the colloid particles or the micelles are shortened, resulting in a drastic contraction and the collapse of the original structure. Consequently, medium pores of 1050 nm could be formed under the above conditions.

Figure 9. Distribution of pore with wide radius

Figure 10. X-ray pattens of samples

3.2.5. pores

Ef fect of successive washing on wide

Wide pores mainly distribute in the range of 300 1000 nm, as shown in Figure 9. It is obvious from Table 5 that different washing conditions could lead to different pore radius and volumes, because of the different assembling behaviors of secondary particles and their aggregates.

188

Yuefeng Yan et al./ Journal of Natural Gas Chemistry Vol. 14 No. 3 2005

In Table 5, we can see that successive washing and intermittent washing have different effects on the pore volumes of wide pores. The volumes of the wide pores basiscally remained constant after intermitant washing for three times, but for the successive washing the situation was the opposite. This difference may be due to the stirring in the first stage of the intermitant washing. Repeated stirring in a washing medium might break the interface between the secondary particles and their relative displacement might change, so that the interspace between the secondary particles was increased and the pore volume was enlarged. Meanwhile, the process of stirring did not exist in the successive washing, and the mutual transferring ratio of the elements in secondary crystals was decreased because of the addition of superfluous ammonia. Therefore, the surface of the pseudoboehmite was covered by the particles, causing a compacting of the structure and the decrease of the wide pore volume. It is interesting to note that the higher the pH, the larger the radius of the wide pores, as shown in Figure 9. This might be resulted from the breaking function of ammonia to the structure of the secondary particles. More ammonia can suppress the mixing of the aggregates, consequently decrease the percent of the water content. Thus, the space and pores radius of pseudoboehmite can be enlarged. Both mixing and additives such as ammonia play the roles of changing the amount of water between the particles and their assemblage by changing the assembling states. Water is one of the simplest and the most important additives, in some sense, it is water that created the space of the molecules. If the amount of water is increased, the porosity of the samples would increase, too. On the other hand, it is water that supports the force between the particles and the aggregates. By bonding with the particles

and the assemblages by the OH groups, water can act as bridges for stabilizing the assembling state of the particles. The more the OH groups, the higher the stability fo the particle assemblages, and the more difficult for the breaking of the wide pore structure. 4. Conclusions The optimum technical conditions for successive washing have been found to be 1 =40 , pH1 =11.3, V1 =150 L/h , t1 = 15 min , 2 =40 , pH2 =9.8, V2 =50 L/h, t2 =15 min. The advantages of successive washing are as follows: (1) alumina yield can be increased to a large extent; (2) production cycle can be shortened greatly; (3) deionized water consumption can be reduced; (4) labor intensity can be lowered. Effects of technical parameters on the pore structure during successive washing have been evaluated, offering information for the preparation of -Al2 O3 supports with diversified pores structures. References
[1] Arabczyk W, Narkiewicz U, Moszyski D. Appl Catal, n 1996, 134(2): 331 [2] Martens W N, Kloprogge J T, Frost R L et al. J Colloid Interface Sci, 2002, 247: 132 [3] Xiang D H, Weng Y P, Li Q Sh. Solid catalyst. Beijing: Chemical Industry Press, 1983. 255 [4] Tsukacha T. JP 08268715 1996 [5] Hou CH L, Liu J, WR Q et al. Transaction Zhongnan Industrial University, 1997, 28(3): 238 [6] Decleer J G M. Bull Soc Chim Belg, 1992, 101(2): 89 [7] Trimm D L, Stanislaus A. Appl Catal, 1986, 21: 215 [8] Fedorov B M, Danyushevskii Y Y, Fialko V M. Kinet Katal, 1992, 33(2): 416 [9] Yan Y F, Zhi J P, Zhang G Y. Gongye Cuihua (Industrial Catalysis), 2005, 13(3): 50