DE1542614A1 - Catalysts based on synthetic aluminum silicate - Google Patents

Description

American Cyanamid Company, Wayne, NoJ >, V «St.A.

Synthetic aluminosilicate based catalysts

The invention relates to a method for reducing the alkali · = metal content and especially the sodium content of synthetic alkali metal aluminosilicates with a rigid three-dimensional lattice structure and uniform pores as well as improved catalysts based on such aluminosilicates »

The synthetic alkali metal aluminosilicates to which the invention relates are substances sometimes referred to as moles = Kularaie or synthetic crystalline zeolites are designated »and in particular those as X- and Y-Zeollthebezeioh ^ Neten synthetic crystalline zeolites, as they are in number patent specifications, e.g. in the USA patent specifications

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2,882,244, 3,140,249, 3,140,253, and 3,130,007.

These alkali metal aluminates are a type of crystalline hydrosilicate zeolite that contain varying amounts of alkali metal (up to 15% by weight and more) and aluminum oxide with or without other metals. The alkali metal, silicon, aluminum and oxygen atoms in these zeolites are arranged in the form of an aluminosilicate salt in a defined and uniform crystal lattice.The structures usually contain numerous small cavities, which are connected by a series of even smaller stirrers or channels. These cavities and channels have uniform QrQBe and have an effective pore diameter of about 6-15 k.

The alkali metal aluminates should have small particle sizes

au / wise, usually with a medium partial ohmic lake less than 15 and preferably 2-12 Micron.

The term " ^N alkali metal" as used in the present context is intended to include aluminum silicate catalysts, such as, for example, sodium, culium or lithium, but substances containing sodium are preferably used as starting materials to which the process is applied.

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As in some of the above-mentioned patents, ZoB.in der U.S. Patents 3 HO 249 and 3 HO 251 are made synthetic aluminosilicates of the type they are used for purposes according to the invention come into consideration in processes for the conversion of hydrocarbons and in particular in catalytic Used for cracking hydrocarbons. Molecular sieves in various matrices, e.g., silica-alumina gels, have been introduced for use in this area and then applied in processes for the conversion of hydrocarbons.

As is generally recognized in the hydrocarbon conversion art, it is essential, if not critical, that the synthetic aluminosilicate have uniform pores 6-15a ^{3 in diameter} Alkali metal content increases the deposition of coke or carbon on the cracking catalyst, which in turn requires frequent regeneration and ultimately a shorter life of the catalyst. This harmful effect of the sodium content8 has been known for a long time and is also clearly expressed in the USA patent 3 HO 249.

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X-Zeolitli can be obtained by the following oxide ratios in mol mark:

1.0 * 0 _f 2M _{2 /} , O: A1 ₂ O ₃ : 2.5 ^ 0.5 Si0 ₂ : _y H ₂ 0

Therein M means an alkali metal, η its valence and Yeiren Numerical value up to 8 depending on the type of alkali detail and the Degree of hydration of the crystal. The sodium form can be expressed in oxide mole ratios as follows:

0.9 N ₁ Si ₂ O 1 ₂ O ₅ : 2.4 SiO ₂ : 6.1 HgO

Y zeolite has the following oxide ratios in moles: 0.9 * 0.2 Na ₂ O: Al ₂ O ₃ : WSiO ₂ : yH _{2 O}

Here w means a numerical value from 3-6 and y a numerical value up to about 9.

It was found that the alkali metal content of
Molecular sieves of the X zeolite type can reduce by using the

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Zeolite continuously or repeatedly for long periods of time subject to a base exchange, for example with solutions of rare earth salts. However, one such method of reducing the alkali metal content of these zeolites is complex and time consuming. Furthermore, devices are unnecessarily used for a long time, which would otherwise could be better used.

With respect to synthetic alkali metal aluminosilicates from Y zeolite type was found to be regardless of the length of the Treatment time or the number of exchange stages as well as the amount of cation exchanger used, but not the alkali metal content can be lowered below certain values.

The aim of the invention is therefore an improved method for reducing the alkali metal content of synthetic crystalline Alkali metal aluminosilicates, of the X- and Y-zeolite ^ type.

The inventive method for reducing the alkali metal » content of crystalline alkali metal aluminosilicates of the X and Y zeolite type, which have a rigid three-dimensional lattice structure and are characterized by uniform pores are, is characterized in that the alkali metal content is partially reduced by base exchange of a portion of the alkali metal, the alumino-

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calcined silicate and the calcined aluminosilicate is subjected to a further base exchange before it is introduced into a matrix. The method of the invention is applied to the synthetic alkali metal aluminosilicate itself. IDs was found in other words, that the application of the method according to the aluminosilicates itself as opposed to a calcination and / or oinem base exchange of aluminosilicates in arrays of inorganic oxides a much easier control of the process allowed and leads to improved Crackkatalyeator.

As can be seen from this, three interrelated procedural stages are required.

1 · You apply one or more first cation or base exchange stages to the aluminous precipitate as such".

2. Calcination of the partially exchanged alkali metal aluminosilicate8 and

3 * further addition of the calcined aluminosilicate, which is subject to a partial exchange.

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The cation exchange can be carried out with numerous salts described below, including a number catalytically active metals are introduced into the synthetic zeolites.

According to a preferred embodiment of the invention as salts for the exchange of salts from rare earths, e.g. Ger, lanthanum, praseodymium, neodymium, promethium, samarium, Europium, gadolinium, terbium, dyaproaium, holmium, erbium, Thulium, Ytterbium, and Luteoium, are used.

Either the salt of a single metal, or preferably of several metals, can be used as the rare earth salts, for example a chloride of a rare earth metal or the didymium chloride. A rare earth chloride solution, as it is referred to below, is a mixture of rare earth chlorides, which essentially consists of the chlorides of lanthanum, cerium, neodymium and praseodymium bit smaller amounts of saarittm, gadolinium and yttrium. The rare earth chloride solution is commercially available and contains the chlorides of a mixture of rare earths with the following relative composition: cerium (as CeOg) 48% by weight, Lanthaa (ale La ₂ O,) 24% by weight, praseodymium (as Pr ₆ O ₁₁ ) 5 wt. #, Neodymium (as Nd ₃ O ₃ ) 17 wt. #, Samarium (as Sm ₂ O ₅ ) 3 wt. #, Gadolinium (as Gd ₂ O ₃ ) 2 wt , Yttrium (as Y ₂ O ₃ ) 0.2 wt .- $ and other rare earth oxides 0.8 wt.

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Didym chloride is also a mixture of Qeltener earth chlorides but with a low cerium content. It consists of the following rare earth metals (as oxides): Lanthanum, 45 - wt. «#; Cerium 1-2 wt .- #, praseodymium 9-10 wt .- ^, neodymium 32 wt .- #; Samarium 5-6 wt .- ^, gadolinium 3-4 wt. = $, Yttrium 0.4 wt .- ^, other rare earths 1-2 wt "- #

It should be noted that other rare earth mixtures are also used for the purposes of the invention can be.

The first ion exchange, ie that which is to lead to a partially exchanged synthetic cation-alkali metal-aluminosilicate, can be carried out in aqueous media at room temperature, but temperatures in the range from 35 ^° C. to the boiling point of the mixture are preferably used is the temperature at which the cation exchange is carried out about 40 bie 60 ⁰ C.

After the partial ion exchange of the synthetic aluminum is calcined ~ minosilikat, for example, at 450-900 ⁰ C with or without Wasserdampfatmosphäre- After calcining the partially exchanged aluminosilicate is slurried in water, and with further salt containing the desired cation, offset, in order to lower the content of alkali metal ions to the desired value.

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As with the first exchange, during the second exchange stage, the aluminosilicate slurry and the cationic acid solution are preferably agitated. Then the slurry filtered and washed with water.

If the aluminosilicate is to be used for cracking catalysts, the alkali metal content is normally reduced to as low a value as possible, based on the weight of the aluminosilicate, and often to an alkali metal content of less than 1 i> with the aid of the process according to the invention.

The partial obtained by the process according to the invention or fully exchanged aluminosilicate can be made with matrices organic oxides, e.g. Silicon dioxide, aluminum oxide, silicon dioxide magnesium oxide, silicon dioxide-aluminum oxide-magnesium oxide by any convenient method, for example united by grinding or homogenizing or introduced into them.

For example, the alumino-oily alumina can be mixed in the desired weight ratio with a suitable inorganic oxide hydrogel, for example with silicon dioxide-aluminum oxide hydrogel with an aluminum oxide content of 5 to 30 %, based on the dry weight

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In such a way of working, the mixture is mixed in a pan mill to produce a uniform mass and then spray-dried. It may be necessary to filter such hydrogel masses in three or more stages in order to remove sodium or other undesired ions therefrom. The fully exchanged molecular sieve can be introduced into the hydrogel after a first or second filtration stage. In such a process, the pH of the aluminosilicate / hydrogel slurry should be adjusted with ammonia and a third washing stage should be used. This is because the washed slurry can be dried, for example, by spray drying. The aluminosilicate can also be introduced into hydrogel cogel masses, or the introduction can be carried out using methods in which aluminum oxide is precipitated on silicon dioxide and the mass obtained is mixed with the aluminosilicate . Such methods are well known in the art - some of which are described in U.S. Patent 5 HO249.

The following examples explain the invention without restricting it. All information about parts and percentages in bees is based on weight, unless otherwise stated .

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~ 11 - Example 1 Exchange with rare earth nitrates without salting

800 g of a wet filter cake of synthetic crystalline aluminoeil ^ inde SK - 30 with a sodium content of 14.7 ^ indicated as Na ₂ O (a synthetic aluminoeilicate old of the above mentioned molecular formula of Y-zeolite) were slurried in 6550 ml of water. In the slurry, 550 g of crystalline rare earth nitrate hexahydrate (40 jfi rare earth oxyä) was dissolved (about 1.1 times the equivalent of the amount theoretically required to replace all of the sodium in the aluminosilicate).

NaOH 30 minutes of mixing at 45 - 5O ⁰ C was filtered, the slurry, and 12, 000 ml Waaeer containing 200 g SelteneB Erdnitrat-contained, washed.

The analysis showed a NagO content of 3.6 _% based on the dry weight of the filter cake.

The filter cake obtained after the first thaw was slurried again in 6550 ml of water and mixed with 550 g of SeI-tenem earth nitrate. After one hour at 40-5O ⁰ C the suspension was filtered again and with 12,000 ml

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Water containing 200 g of rare earth nitrate, washed *

The analysis of the filter cake showed an Na ₂ O content of 3.7-6, based on the weight of the cake.

The procedure described above was repeated except that the slurry was removed before filtration. Was stirred for 50 ⁰ C - 2 hours at 40th No rare earth nitrate was added to the wash water.

The analysis showed a NagO content of 3.5 #, based on the! dry weight of the washed filter cake?

Example 2 Exchange with rare Brdohlorid without caulking

The same procedure (including the same synthetic zeolites) and the same amounts were used as in Example 1, with the exception that instead of the nitrate used in Example 1, the slurry was mixed with 485 g of rare earth chloride heatabydrate (yields 45% when calcined) ^c /> rare earth oxide) and 175 g rare earth chloride (45 # rare earth oxide during calcination) was added to the washing solution ο

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The mixing time before filtering was 24 hours for the first exchange, 16 hours for the second exchange and 3 hours for the third exchange.

The NagO analysis at the end of each of the three replacement procedures gave 3.6 #, 3.3 # and 3.1 # based on the weight of dee washed filter cake «.

Example 3

First exchange. Calcining and renewed replacement of Y zeolite aluminosilicates

Synthetic aluminosilicate (Linde's Y molecular sieve (SK-3O) as in Examples 1 and 2) was exchanged once according to the procedure of Example 2. The wet filter cake was introduced into a hot rotary calciner with a dumbbell temperature of 65O ⁰ G (120O ⁰ P).

Water vapor was introduced into the calciner from behind. The bed temperature was raised to 650 ° O (1200 ⁹ F) and held at this temperature for 10 minutes. The batch was then applied.

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1 kg of the calcined partially exchanged molecular sieve was slurried in 8730 ml of water. An amount of rare earth chloride equivalent to the theoretical amount of sodium originally present in the aluminum inosilicate was then added. After 30 minutes at 40 ~ 55 ⁰ C the slurry was filtered and washed free of chloride, as was determined by the silver nitrate test in the piltrate.

The analysis showed an Na ₂ O content of 1 »25 ° ß> ₉ based
on dry weight.

In order to demonstrate the importance of rapidly and smoothly reducing the sodium content of synthetic zeolites which are to be used for catalysts for cracking hydrocarbons, an activity comparison of catalysts prepared according to the procedure of Examples 1 and 3 with a conventional one was commercially available available silica-alumina catalyst with 13 $> aluminum oxide (fluid cracking catalyst) was carried out using a recognized standard test method.

cd In the test method, 30 ml of gas oil were used in a time of

- * 15 minutes passed through a plague bed of 50 ml of catalyst deactivated with steam ^. The catalyst was _m in a pipe using a muffle furnace to

^ 1 ⁰ C (940 ^ 2 ° 1 ^J ). The gas oil was from above

down through a preheat section of the catalyst tube and passed through the catalyst bed. The product vapors were cooled. The liquid condensate obtained

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was collected in a container while the uncondensed gases were sampled with a wet test meter and were dosed.

The liquid product (digested Gaa oil) was distilled using a 125 ml Engler flask. The distillate was collected to the point where the vapors reached 204 ° 0 (400 ⁰ P) «,

The gas sample was mass spectrometry for its different Components examined *

The results of this comparison are in Table I below listed ,,

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3-SiO ₂ Table I. 750 ° C. 40 activity G »P. CF. C. t
5 sample 1 ^ Catalyst pretreatment conversion 750 ° C. 57 38 0.93 1.67 1 , 03 13 tf Al ₂ O • χ (h) Steam,
17 hours 750 ° C. 57 58 0.64 0.44 1 , 18 example Steam,
17 hours 62 0.49 0.45 1 , 25 example Steam,
17 hours

(a) Aluminosilicates - prepared as in Example 1 and then washed with washed before spray drying ° 13 £ AlgO ^ -SiOg-Orack catalyst mixed; Catalyst contained £ 5 rare earth Y zeolite,

<o based on the Katalyeatorgeeamt weighted. §

• '■ - J

- »(b) Aluminosilicates - prepared as in Example 3 and then mixed with washed · ^ 13 i> Al ₂ O ^ -SiOg crack catalyst before spray-drying; Catalyst contained 5 $ rare earth Y zeolite,:

- · based on the total weight of the catalyst. <n.

<** G.?.· The gas factor is the ratio of de · "at standard conditions (dry gas, 20 ⁰ C, 760 mn" "* Hg) Ftüfkatalysator Garroluaen produced to the same conversion generated by the standard catalyst gas volume.

C.F. * The carbon factor gives the ratio of the carbon yield obtained with the test catalyst to the carbon yield obtained with the standard catalyst with the same conversion

Cjp The C ₅ factor is the ratio of the yield of end compounds achieved with the test catalyst (up to 204 ⁰ O (40O ⁰ P) normal boiling point; debutanized) to the yield of C ₅ + compounds obtained with the standard catalyst with the same conversion.

* - explained in American Cyanamid Company "Test Methods For Synthetic Fluid Cracking Catalyst" 1st ed. P. 58..

From Table I it can be seen that with catalysts that

contain crystalline aluminosilicate exchanged according to the invention, a higher yield of gasoline can be achieved, as the Ce ⁺ ~ oil actuator indicates

Example 4 Replacement of sodium aluminosilicate of the Y zeolite type after Calcining

Synthetic aluminosilicate (Hnde's Y molecular sieve SK-30) with a moisture content τοη 60 t (supplied to) was calained as described in Example 3, without an exchange being carried out before the calcination.

2 kg of the calcined product was slurried in 38.5 liters of water. Then 1.1 times the amount of rare earth nitrate was added to the theoretical amount of sodium in the aluminosilicate. After 60 minutes, the slurry was filtered off and 45.4 liters of warm water were washed.

The washed filter cake was exchanged a second time using the same amounts of water and rare earth nitrates.

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The analysis of the washed filter cake resulted in a hold of 5.6 #, based on the dry weight

As the above procedure shows, calcination prior to ion exchange is not effective in removing Suitable for sodium.

Sine sample of the twice-exchanged and washed aluminosilicates described above was mixed with washed silica-alumina hydrogel with 15 i> AIuminiumoxyd and spray dried (weight dry * · as shown in Table I) is a cracking catalyst with 5 $> exchanged molecular sieve obtained.

The results are given in Table II.

Table II

Sample Katalyeatorvorbe- VRF / end- Aktiv! - GP · CF. Ö _K ⁺ action ^XQn ^ tat *

Example water vapor, 58 57 0.98 1.07 1.02 ₇ 750 ⁰ C
'17 hours

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As can be seen iBt ouch Tables I and II, are catalysts calcined before Austauach aluminosilicate included, compared with a silica-alumina-Standardkatalyaator with 13 1 "aluminum oxide no advantages.

Example 5 Replacement of rare earth Y molecular weight with ammonia

Linde's sodium Y molecular sieves (SK-30) were made as in Example 3 exchanged with rare earths and calcined.

406 g of the calcined molecular sieves were slurried with 106 g of NH.Cl in 3,500 ml of hot water. Post-40 minutes at 50 - 65 ⁰ C with stirring, the slurry was filtered and washed free of chloride bia dea filtrates.

The analysis showed, based on the dry weight, 19 # 4 $> SE ₂ O ₃ ,, 1.35 # Na ₂ O and 1.9 $> NH ,.

Example 6

Exchange of ammonia of rare earth Y molecular seeds

Wash with NH.C1

Low sodium Y molecular sieves (SK-30) were made as in Example 3 exchanged with rare earths and calcined,

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4! "5 kg (10 pounds) of the calcined partially exchanged molecular sieves were slurried in 41 kg (90 lbs) of water at 6O ⁰ C (14O ⁰ P). 3.3 kg (6.2 lbs) of rare earth chloride hydrate were added to the slurry. After stirring for 45 minutes, the slurry was filtered off and washed with 5.4 kg (12 pounds) of water. The pilter cake was drained and then washed with 26.3 kg (58 pounds) of a 3% ammonium chloride solution. Finally the cake was washed with 150 kg (330 lbs) of water.

The analysis revealed based on the dry weight, 21.0 f "SE ₂ O ,, 0.8 96 Na ₂ O, and 2.1 96 NH-.

As can be seen from Examples 5 and 6, the sodium content in the exchange made after calcination can be effectively reduced using ammonium salts alone or in combination with salts of rare earths.

Example 7 Exchange of aluminosilicates of the X-zeolite type with Rare earth chlorides

36 kg (80 lbs) wet cake of a linde 13X aluminosilicate molecular sieve (Zeolite X type) were in 390 kg (860 lbs) of water slurried. Then 31 kg (68 lbp)

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Rare earth chlorides (1.1 equivalents of the theoretical amount of sodium originally present) added to the slurry. After one hour at 52-54 ⁰ O (125-130 ⁰ P), the slurry was filtered and washed. The washed filter cake was exchanged again as above, a total of four times (the NagÖ analysis, based on the dry weight of the filter cake, after the individual exchange stages showed 3.4 »1.5, 0.9 or 0.6 i» ₀ ) .

Example 8

Renewed exchange of partially exchanged rare Brd -X zeolite molecular sieve after calcination

A sample of the filter cake from Example 7, which was replaced four times, was ^{dried at 121 0} O (250 ⁰ F) for 24 hours and then calcined. For this purpose, the dried sample was introduced into a cold rotary kiln and then ^{heated to 650 °} C. (1200 ^° F.). During the calcination, steam was introduced into the kiln. After 10 minutes at 65O ⁰ O (1200 ⁰ F) the batch was discharged.

88 g of the calcined aluminum silicate were In 850 ml Slurried water and mixed with 71 g of rare earth chloride (approx

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1.1 "times the theoretical amount, based on the original sodium content of the original aluminiumailicate). After mixing for 30 minutes at 45-5O ⁰ C, the slurry was filtered and washed free of chloride.

The analysis of the filter cake showed, based on the dry weight, $ 0.10> sodium oxide _e.

Example 9

Renewed exchange of partially exchanged rare items · » Earth-aluminobilicate of the X-zeolite type naoh Kaie! Kidneys and in Absence of water vapor

332 g filter cake of a molecular sieve of the X-zeolite type (Linde 13X) were slurried in 3000 ml of water and mixed with 283 g of rare earth chloride (1.1 times the theoretical amount). After 30 minutes at 45-5O ⁰ C the slurry was filtered and washed with 5000 ml of water.

The filter cake was naoh the same working method and the same amounts of water and rare bromide chlorides as exchanged again in the first exchange stage · The The slurry was filtered and released until it was free of chloride

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of the filtrate washed.

The analysis showed, based on the dry weight of the original filter cake, 2.5 liters of sodium oxide.

About 1/4 of the resulting filter cake became a third Exchange with 1/4 the amount of water and rare earth chlorides subject.

Analysis of the washed filter material showed related on the dry weight of the original filter cake,

1.5 ° / ° Na ₂ O.

The remaining sample from the second Austauachstüfe was dried for one hour at 180 ⁰ G and then 10 minutes at 595-621 ⁰ C (1100 »1150 ⁰ F) calcined without the use of a steam atmosphere. 88 g of the calcined aluminosilicate were exchanged using 850 ml of water and 71 g of rare earth chloride. After 30 minutes at 45-55 ° G, the slurry was filtered and washed until the filtrate was free of chloride.

Analysis found $ 0.23> sodium oxide based on that

Dry weight of the original filter cake »

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Claims (4)

- 24 claims ./ Process for exchanging the alkali metal content of crystalline alkali metal aluminosilicates of the X and Y zeolite type _# characterized in that the alkali metal cation is partially exchanged, the partially exchanged aluminosilicate is calcined and then the alkali metal content of the partially exchanged calcined aluminosilicate is reduced further by a further ion exchange. 2. The method according to claim 1, characterized in that the alkali metal cation is partially counteracted before the calcination exchanges a rare earth metal. 3. The method according to claim 1, characterized in that an alkali metal aluminosilicate from the X or Y zeolite ^ Type used, which is finely divided and a rigid three-dimensional lattice structure and uniform pore openings ο
with 6 - 15 A. 4. The method according to claim 1, characterized in that the alkali metal aluminosilicate is a sodium aluminosilicate used, this a partial exchange with a 009814/1567 ... 25 - Rare, earth metal subjugates, and then calcined subjected to another exchange of sodium for a rare earth metal. 5 × The method according to claim 1, characterized in that exchanging the alkali metal cation partially, that introducing the aluminosilicate in a matrix of an inorganic oxide and a composition, in that calcining the composition and then subjecting it to further reduce the alkali metal content to a further exchange . 009814 / 1SIT