JPH02501567A - Method for producing modified zeolite Y - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method for producing modified zeolite Y Background of the invention The present invention has enhanced stability and preferably also small zeolite unit cell dimensions. First, it relates to a method for producing modified (transformed) zeolite Y.

Applications of zeolites, especially as catalysts in petroleum processing, especially for the production of so-called middle distillates increased stability and particularly small unit cell dimensions or It is known that the size ao improves the performance as a catalyst (for example, (See U.S. Pat. No. 4,419.27L).

In view of these results, different methods can be used to increase the stability, especially for synthetically obtained units. Make the cell size (usually ao = 24. [i3 to 24.70 people) as small as possible. Efforts have been made to

For example, UK Patent Publication Section 2. H5,86L is ammonium ion The combination of ion exchange process and aluminum ion exchange process allows zeolite NaY to be It shows what can be modified. This treatment increases the catalytic activity and increases the unit cell size. It seems possible to reduce the number to 24.45-24.52 people. deer However, this production method has a low degree of residual ion exchange ( Resultual exchange degree) discovered.

British Patent Publication No. 2.014,970 discloses that 550 to 800 A two-step ammonium ion exchange process step with an intermediate calcination process step at ℃ That's what you get. Unit cell dimensions or size aO is 24.2Q to 24.45 Ultrahydrophobic zeolite (ultrahydrophobjeolite)

11te) is disclosed.

European Patent No. 0.028.938 discloses that hydrocarbons boiling above 371°C, Midbarrel fuel oil with a distillation range of 149-371”C discloses the use of modified zeolites for selective conversion to fuel) products. Ru.

British Patent Publication No. 2,114.594 discloses that the method is calcined in high-temperature steam. unit cell size in the range of 24.38 to 24.58 people, especially smaller than 24.40 people describes the selective production of middle distillate hydrocarbons by the use of modified zeolite Y with ing.

The present invention involves calcination in steam (steam) at 400-900°C after the ion exchange process step. It should be noted that increased stability can be obtained by performing In contrast, calcination at 400 to 450°C only provides stabilization. Ammonium ion exchange process step and aluminum ion exchange process step In addition to performing aluminum ion exchange process steps, ammonium ion exchange Both the processing step and the calcination step are preceded by the aluminum ion exchange step. followed by an atmosphere saturated or substantially saturated with water vapor (steam) at 500-900°C. Calcining at 500-900°C is stable if the calcination process step is carried out in an ambient atmosphere. Based on the insight that, in addition to increasing the It is something to put.

By proceeding the process in this way, the number of process steps and/or The desired small unit cell size can be achieved with a shorter overall operating time.

The present invention also allows the unit cell size to be less than 24.20 people; This is something worth noting.

British patent published for combination of ammonium ion exchange process step and calcination process step In the conventional modification of zeolite Y described in Section 2.014.970, the It is possible to obtain a unit cell size of 24.25 people by calcination for 18 hours at be. Even if the calcination time is extended to 42 hours, the unit cell size is 24.25 people. cannot be made smaller. 24. Calcination at 600℃ for 1 to 18 hours. 35 people only give a lower bound unit cell size. Using the method according to the invention The desired reduction can be achieved more quickly.

Summary of the invention Characteristic features of the invention are set out in claim 1. When applying the present invention, If you only want to maintain or stabilize the temperature, perform the final calcination at 400 to 500℃. The reaction can be carried out at a low temperature, preferably from 400 to 450°C. The calcination time is preferably 0.25 to 5 hours; shorter calcination times are used at higher temperatures. You can also do that. Calcination times shorter than 0.25 hours give inferior effects, while calcination times shorter than 5 hours Long calcination times do not significantly enhance the locking effect. Both fixed and decreasing unit cell dimensions The final calcination must be carried out at a temperature of at least 500°C. No. In that case, the calcination time would be the same 0.25-5 hours. Suitable calcination time The duration is at least 45 minutes.

Brief description of the drawing The invention will be explained by the following examples with reference to the accompanying drawings. In the attached drawing 1 and 2 show a comparison between the present invention and the prior art. Third Figures 9 to 9 show process flowcharts. Of these, Figures 3 and 4 show the prior art. 5-9 show various embodiments of the invention.

Description of the preferred embodiment Example 1 In this example, the zeolite NaY contains water, alumina, silica and sodium hydroxide. It was made as usual from lium. The obtained zeolite NaY has a molar ratio of 5i 02/Ai 03 is 5.0, and Na2O is equivalent to 13.4% by weight. Ta. This zeolite NaY used as a starting material has a HOm/g (BET : p/po = 0.15) and the specific surface area of 24.87 people (A S T N : with unit cell dimensions (measured by XRD in accordance with D.3942-80). there were.

Next, the zeolite used as a starting material was ionized with lθ% aluminum sulfate solution. The content of Na2O was changed to 2.8% by weight. Next, deionize the washing solution with deionized water. It was washed until it contained no acid ions. The zeolite was then dried at 100°C to completely remove the zeolite. The solid content was 80-90%. At this point, dry zeolite is heated to 600°C steam (water The mixture was calcined for 2 hours in an atmosphere saturated with steam. At that time, the unit cell size is 24.5 The number was reduced to two.

The next process step is ion exchange with ammonium sulfate ions, similar to the method described above. The Na2O content was reduced to less than 0.25% by weight. child At the time point, the zeolite thus treated was treated with an aluminum sulfate solution (concentration 0. (NH4)2 of the zeolite by ion exchange (1-8%, typically 5%). 0 content was reduced from 3.0-4.5% by weight to 1.5% by weight. In the table below The reported results are based on ion exchange with aluminum sulfate solution having a concentration of 8% by weight. What you get for something that has been exchanged.

It is. Ion exchange site in zeolite per mol in solution The amount of AU'' was 8 moles.

At the end, the zeolite thus treated is dried and placed in an atmosphere saturated with water vapor. Calcinate at medium temperature of 500-900℃ and reduce unit cell size to 24.15-24.35 people. I let it happen. A flowchart illustrating this process is shown in FIG.

Final unit cell dimensions after aluminum ion exchange and subsequent calcination in steam The method was found to depend on the amount of aluminum ions supplied by ion exchange. It was.

Under certain calcination conditions, the amount of aluminum ions supplied by ion exchange is The greater the number, the greater the reduction in unit cell dimensions. Table 3 shows AJ) “ion exchange The test results are shown when both the degree of exchange and the calcination time were changed.

For comparison, zeolite NaY produced as a starting material was washed with water, dried, and annealed. Monium ion exchange, calcining, further ammonium ion exchange, and finally drying. In addition (see FIG. 3), zeolite USY of the prior art was manufactured. In this case, calcination and ion exchange process steps were performed as described above. Known zeolite USY In order to compare the product according to the invention with the zeolite, water at the temperatures indicated in Table 4 A final calcination was carried out in steam.

Unit cell dimensions a obtained under various conditions. The results are shown in Figures 1 and 2 and Figures 1 and 2. Shown in the table.

As shown in the results shown, when using the method according to the invention, 24. Unit cell sizes ranging from 15 to 24.35 people are obtained more quickly.

Table 1 Table 2 shows a comparison of two zeolites produced according to the invention. One of these days One type is aluminum ion exchanged and heated at 650°C before the aluminum ion exchange. (Fig. 6); in contrast, other types of zeolite The emitting material is ordinary zeolite USY made by the conventional method as described above. At the end, after the drying process step, it undergoes aluminum ion exchange and then heat treatment. It was calcined in an atmosphere saturated with water vapor at 650°C (No. 7 figure). From Table 2, it can be seen that during calcination in a steam atmosphere and aluminum ion exchange, It is clear that the same results are obtained regardless of whether or not ammonium ion exchange is performed. It's turning into a crab.

Table 2 Table 3 Example 2 (comparison) In this comparative example, a thermally stabilized aluminum ion exchanger The converted zeolite Y was prepared according to the implementation of British Patent Publication No. 2.01115.861. Made essentially according to the instructions given in Example 1.

As a starting material, the same zeolite NaY as in Example 1 of the British Patent Publication was used. This starting material was prepared according to process step 1v(a) of Example 1 of the GB-A. It was treated in three ion exchange steps. 10% by weight of ammonium sulfate each time The process was continued for 30 minutes at 60-80° C. with ammonium sulfate solution. this After ion exchange, the zeolite contained 3.2% by weight Na2O. then 6 Calcining was performed at 50° C. for 3 hours to obtain a calcined product. This product was then published in the UK Patent Publication No. Exactly follow process steps (b) and (C) of Example 1 of Publication No. 2.085.861. I processed it. That is, in process step (b), the product is first treated with 0.05M alkaline sulfate. pH 3,3 for 45 min with ammonium sulfate solution followed by dilute ammonium sulfate solution. The sample was subjected to ion exchange treatment twice. This ammonium sulfate solution contains 10% by weight of ammonium sulfate. It contains ammonium, and was used at a temperature of 60 to 80°C for 30 minutes in each treatment. subordinate Therefore, this processing schedule corresponds to the schedule according to FIG. 4 of the attached drawings.

Another batch of starting material was prepared according to process step (a) above for use as a reference sample. Processed. However, the subsequent ammonium ion treatment was performed only twice. won.

Each run was continued for 30 minutes at 60-80°C using dilute ammonium sulfate solution. Obtained The reference sample contained 0.42 wt% Na2O and had a unit cell size of 24.52 people. It had a molar ratio of Sl02/A4203 of 5.0. This processing schedule The schedule essentially corresponds to the schedule of FIG. 3 of the accompanying drawings.

The measured properties of these various products are shown in Table 4. Table 4 also includes , British Patent Publication No. 2,085. [Includes values obtained from Example 1 of Publication No. 1] There is. Table 5 shows the degree of AU” ion exchange after process steps (b) and (C). It is. This degree of ion exchange means that in the reference sample state, all available ion exchange The site is occupied by ammonium ions and sodium ions. aluminum ions and sodium in process steps (b) and (C). Assuming that only thorium is affected by ammonium ion exchange, It is calculated. In the reference sample and in the product after aluminum ion exchange , and after two ammonium ion exchanges during process steps (b) and (C). Measure the number of moles of ammonium ions and sodium ions in the product, and was used to calculate the percentage.

These results indicate that the two rounds of ammonium ion exchange were performed in advance by ion exchange. Ion exchange of all or most of the aluminum introduced into the zeolite This indicates that this caused the zeolite to be expelled to the outside.

The change in ion exchange degree is estimated to be due to crystal changes and changes in unit cell dimensions. It will be done. The residual amount of aluminum in the ion exchange site has an effect on the unit cell size. It's not enough for me.

Table 4 Table 5 Example 3 In this example, aluminum ions supplied by ion exchange were How can it be fixed using the present invention without bringing about a significant change in the law? Indicates whether the person is capable of

In this example, the final calcination in steam was performed for 45 minutes and 40 minutes in the production of the product of the present invention. Example 1 was repeated except that it was carried out at 0-450<0>C. In other words, in Figure 9 Manufacturing was carried out according to the schedule. °For inspection analysis, a conventional design for comparison Olite USY was subjected to the same steam calcination and contained 10% by weight of ammonium sulfate. Ammonium ion exchange with ammonium sulfate solution at 60-80℃ for 30 minutes I did that once. The results are shown in Table 6.

The results in Table 6 show that in the conventional zeolite USY, the amount of energy that was expelled during steam calcination was All the N When using the present invention, namely, NH4+ exchange and water vapor temporary at 400-450℃. When performing A-3+ ion exchange during heating, only part of the ion exchange site is replaced with N. The remaining ion exchange sites are shown to be reoccupied by H4. occupied by Al1- ions fixed during steam calcination. unit cell dimensions It is presumed that the difference is due to AJ'+ ion exchange.

Table 6 In the examples above, ammonium sulfate and aluminum sulfate were used in the ion exchange process. used in stages. Scales with other types of salts such as chlorides and nitrates will be understood by those skilled in the art.

In the examples, a steam (water vapor) saturated atmosphere was used for calcination. but However, the result will not be as good, but it will not be completely saturated with steam (water, steam). It is also possible to carry out the calcination in an atmosphere that is not heated.

Tamagaki investigation report

Claims (10)

[Claims] 1. Zeolite NaY is produced through a series of process steps, namely ammonium subjected to ion exchange, calcination, aluminum (III) ion exchange and drying, Contains aluminum supplemented and fixed by ion exchange, preferably also small In a method for producing modified zeolite Y having unit cell dimensions, The zeolite is further added after the aluminum(III) ion exchange step. The calcination process step is at least 400-900°C water vapor. Consolidation of aluminum ions replenished by ion exchange carried out in an air atmosphere The manufacturing method described above, characterized in that the manufacturing method is characterized in that: 2. At least said additional calcination step is carried out at 500-900°C, According to the amount of aluminum replenished by replacement, the unit cell size is 24.1. The manufacturing method according to claim 1, characterized in that the thickness is reduced to 5 to 24.35 Å. 3. Aluminum ion exchange reduces the (NH4)20 content of zeolite to 1.5 wt. 3. The method according to claim 1 or 2, characterized in that the Production method. 4. Ammonium ion exchange is performed using ammonium chloride, ammonium nitrate, or Claim 1, 2 or 3, characterized in that the method is preferably carried out with ammonium sulphate. 3. The manufacturing method described in 3. 5. Aluminum ion exchange with aluminum chloride, aluminum nitrate, or Any of claims 1 to 4, characterized in that it is preferably carried out with aluminum sulphate. The manufacturing method described in Crab. 6. Claim 1, characterized in that the calcination is carried out in an atmosphere saturated with water vapor. 5. The manufacturing method according to any one of 5 to 5. 7. Specifically, aluminum ion exchange is carried out on ultrastable zeolite Y. The manufacturing method according to any one of claims 1 to 6, wherein: 8. Zeolite NaY undergoes the first round of ammonium ion exchange and then water evaporation. calcined in an atmosphere saturated with air, followed by ammonium ion exchange. It undergoes aluminum ion exchange and is finally calcined in an atmosphere saturated with water vapor. The manufacturing method according to any one of claims 1 to 7, characterized in that: 9. Said additional calcination is at a temperature of 400-500°C, preferably 400-450°C. The manufacturing method according to any one of claims 1 and 3 to 8, characterized in that the manufacturing method is carried out. 10. Calcination performed prior to aluminum ion exchange is performed at a temperature of 500 to 900°C. , preferably carried out at 550-750°C. The manufacturing method described in any of the above.