SU1614757A3 - Method of producing ferrierite - Google Patents

Abstract

The invention relates to catalytic chemistry, in particular the preparation of a ferrierite, a precursor of a dewaxing catalyst. The goal is to increase the activity of the catalyst. To this end, an aqueous mixture containing silicon, aluminum, sodium and piperidine compounds is maintained in the following molar ratio in terms of metal oxides: SIO ₂ / NA ₂ O = 7.69-14.29

SIO ₂ / AL ₂ O ₃ = 18.52-23.36

water / sio ₂ = 10.4-41.4

piperidine / SIO ₂ = 0.2-0.8, at 150-160 ° C until crystals form within 11-20 hours. In this case, the resulting product from sodium ferrierite as a catalyst shows better activity in the specified process than the product from ferrierite sodium, crystallized more than 20 hours. 4 tab., 5 Il.

Description

The invention relates to methods for producing ferrierite, which is a catalyst for the dewaxing of mineral lubricating oils.

The aim of the invention is to obtain. the a dewaxing catalyst with increased activity due to a certain time for the mixture to form crystals.

FIG. Figure 1 shows the test data on the activity of aluminosilicates obtained from the initial mixtures with compositions both within the specified range and outside it for the molar ratio of alumina and sodium oxide to silicon oxide; in fig. 2 is a graph of the catalytic activity of hydroferrierite obtained using ion exchange of sodium ferrierite crystallized at a constant SiC ratio (in the initial mixture; Fig. 3 is a graph of the catalytic activity of catalysts obtained -IF of sodium ferrierite obtained from a formulation in which The sodium oxide in the original aqueous mixture is constant, for example, SiO2 (Na20 25.0) 2.48 (the catalyst activity greatly depends on both the level of sodium oxide and the level of alumina, respectively but the level of silicon oxide, both of these molar ratios must be in a certain range in order to achieve a significant decrease in temperature

SG5

(mA

4 SM

a reactor to reach a solidification point with lubricating oil -6,); in fig. 4 shows a graph of continuous hydrothermal treatment of an aluminosilicate as soon as crystallization begins, line L displays a hydroferrier catalyst, half according to the proposed method, while line B shows the catalyst obtained in the prototype (Extended hydrothermal treatment may actually serve as an obstacle to the activity of the resulting catalyst if a very high crystallization rate will also be achieved; it is shown that if alumina and sodium oxide are held in the correct moles GOVERNMENTAL ratio x, the crystallization time of the starting material of catalyst is reduced to 12 hours in preti- vopolozhnost previously-known process, which required about 113 hours to the crystallization of sodium ferrierite, the latter figure also shows the formation na.bystroe sodium ferrierite after the start of crystallization); in fig. 5 is an example of a group distribution ak; for experiments 50-55, which are derived from the condition of stopping the hydrothermal treatment at 20 hours or earlier, experiments 50-53; show significantly better activity: than testing catalysts derived from sodium ferrite, crystallized; more than 20 h.

I

Example 1. In these experiments, use the cosiness recipe for synthesis with molar ratios,) Na., 0 (HiO) piperidine, equal to 25.0 / xx / yy / 518 / 9.8, in which the amount of alumina is xx, and the amount of sodium oxide is equal to yy. These quantities of XX and yy are given in table. 1 for each experiment. All these compounds are more conveniently added to the autoclave, equipped with a stirrer, and heated to a temperature of 155-160 ° C, which is maintained for 16 hours. After cooling, the contents of the autoclaves are filtered, washed. water, dried at 125 ° C overnight, and then calcined in air in order to remove precipitated amine “Synthetic sodium ferrierites are converted to the hydrogen form by exchange with ammonium nitrate, and then subjected to calcination and ion exchange with tetraamine palladium dinitrate

in the following way. A given amount of sodium ferrierite is subjected to reflux shih for 1 h with 6 n. ammonium nitrate solution in the ratio of 10 ml of nitrate solution per 1 g of dry sodium ferrierite. The hot solution is filtered off, and the filter cake is washed with 10 ml of water per 1 g of dry sodium ferrierite. The cake of the second stage of reflux is then dried (generally overnight) at-125 C. The dried ammonium ferrierite is stirred at room temperature with tetraammonium paladium nitrate solution for 2 hours, washed and dried overnight at 125 ° C. The dried material obtained as a result of these procedures is calcined in air for 2 hours at 550 ° C. The resulting catalysts are then tested for catalytic activity in the dewaxing of hydrotreated, extracted with phenol, light Arabic oil 100 (ABL) with a pour point and chemical components:

a pour point density of 848.6 kg / m.

Elemental analysis, wt.%: With 86,10; H 13.79; N 11 ppm (ppm) 980 ppm.

The conditions for dewaxing are as follows: pressure 85 bar with hydrogen to oil ratio 900 l / standard conditions / kg - at hourly volume velocity of liquid 1.0 kg. Table. Table 1 lists the relative molar content of alumina and sodium oxide per 25 moles of silica, which are used to crystallize the catalyst precursor sodium ferrierite, from which the hydrogen forms of the ferrierite are obtained. Cs corresponds to 1G (no amount of sodium oxide and alumina are given in Table 1.

Under these process conditions, temperature is required to reach the pour point of the dewaxed oil to (-6.6 ° C).

The specified range is achieved only by maintaining the values of sodium oxide and alumina indicated in experiments 12569 10,20,21,23 and 29. If it is necessary to determine the critical parameters ,. activity tests are carried out by

dewaxing oil from arabian oil. The highest catalyst activity is noted at the lowest reactor temperatures. Although it is desirable to have a crystallinity close to 100%, it is permissible to work using a de-araphinization catalyst with a crystallinity less than tOO%, as long as the activity is sufficient to achieve the intended solidification temperatures.

The catalyst, in which mordenite is present in addition to ferrierite, exhibits an initial activity comparable to that of pure hydroferrierite, but the viscosity of the dewaxed oil was lower than that of the dewaxed oil obtained from

Example 3. The example is carried out in order to establish the effects of continuous hydrothermal treatment on the activity of the catalyst in the form of a hydroferrierite. After the crystallization of sodium ferrierite has been completed. The recipe of Example 2 (3KcnepiiMeHT 1.) is used for the optimum range. A hydroferrite catalyst prepared from sodium ferrierite is tested to test the ability to dewax the Arabian oil, reduced to 5%, for the same test conditions as specified for test catalysts 1-7 20 and 2t. Table 3 shows the results of these tests. Example 4. This example is still 10

pure hydroferrieritic catalyst catalyzes changes in water concentration and

amine, which may occur while ensuring acceptable quality ferrite erite

ra.

Example 2. In this example, the raw materials of the catalyst in the form of sodium ferrierite are obtained using a central portion of the predetermined range with respect to the content of sodium and aluminum. The recipe is correlated with example T, in which the initial mixture contains Si02./Al, 0.0325.0:1.07 ;.SiO/Na20 before crystallization; 25.0: 2.48; piperidine 25.0 (518) 9.8.

The crystallization time is varied for experiments 36-49 and ferrierite (if crystallized) is analyzed by x-ray diffraction image. The results are shown in Table. 2

The crystallization time is an important parameter for obtaining pure sodium ferrierite, although, as soon as a duration of 10–20 has been reached (again in the indicated molar ratios of aluminum and sodium), continuous crystallization is not productive, i.e. hydrothermal processing can continue without interruption without affecting the quality of the sodium ferrier, as indicated by an x-ray diffraction pattern. These data confirm the crystallization time shown in FIG. 4. It should also be noted that sodium ferrierite, extracted for 13 hours, is of very high quality and the hydroferrierite obtained from it exhibits extremely high activity.

Example 3. The example is carried out in order to establish the effects of continuous hydrothermal treatment on the activity of the catalyst in the form of a hydroferrierite. After the crystallization of sodium ferrierite has been completed. The recipe of Example 2 (3KcnepiiMeHT 1.) is used for the optimum range. A hydroferrous catalyst obtained from sodium ferrierite is tested to test the ability to dewax the Arabian oil given above for those same test conditions as specified for test catalysts 1-7 20 and 2t. Table 3 shows the results of these tests. Example 4. This example is still

changes in water concentration and

amine, which may occur while ensuring acceptable quality ferrierite "

Ferrierites are synthesized analogously to Example 1, using a synthesizing composition with polar SL / M-Oe / NagO / HrO / piperidine 25.0 / 2.48 / 2.80 / xx / y ratio, where the molar amount of water is is xx, and the molar amount of piperidine is yy, as shown in Table 4.

The synthesis condition includes a synthesis time of 20 hours at 150 s. Crystalline ferrierite with a crystallinity of 90-100% achieved in each case.

Claims (1)

Invention Formula A method for producing a ferrierite, a precursor of a dewaxing catalyst, by keeping an aqueous mixture containing silicon compound, aluminum compound, sodium compound and piperidine in a molar ratio, in terms of oxides, silica:: sodium oxide 7.69-14.29, dioxide silicon: alumina 18.52-23.36; water: silica 10.4-41.4; piperidine: silica 0.2-0.8. at TZO-TbO C until crystals form, followed by separation of crystals, characterized in that, in order to obtain a dewaxing catalyst with increased activity, aging is carried out for 11-20 hours. table 2 777 518 440 363 285 518 eleven eleven II Table 3 Table 4 105 100 101 99 90 111 102 TOO 105 - -3. -g -1 12 3 Fg / g / W 2,0 3,0 ttfl Wj " five 251 0.50 0.70 About 20 30 0 50 war to t but t FIG. Fig.Z / О 10 20 30 НО 50 60 70 80 90 100 110 120 5