DE2042730A1 - Faujasite loaded with rare earths and chromium, process for its production and catalysts made from the faujasite - Google Patents

Description

Grace & Co »(Prio August 29, 1969 2-042730

New York, N.Y. / V.St.A. Hanburg, August 18, 1970

loaded with rare earths and chromium? Faujasite, Process for its production as well as from dsm Fanyasite made catalysts

The invention relates to a synthetic faujasite m

which when used as a promoter for hydrocarbon conversion catalysts has an exceptionally high activity and selectivity.

It is known that zeolites such as synthetic faujasite with a silicon dioxide: aluminum ratio of about 2.5: 1 to 6.0: i can be combined with an inorganic amorphous matrix to form a highly effective hydrocarbon conversion catalyst. These catalysts usually contain between about 5 and 50 sqm.% Zeolite and are usually referred to as catalysts with zeolite activator. These catalysts have a particularly high activity for catalytic cracking processes, and for a given feedstock they selectively provide a high proportion of the desired end products.

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Attempts have been made to modify the activity and selectivity of these catalysts the structure and the composition of the zeolite & u increase. For example, zeolites and in particular faujasites are subject to an exchange with a wide variety of metal cations and thermal as well as chemical treatments have been exposed to their thermal stability and to improve their catalytic properties "

Among other things, it has already been found that Faujasite after an exchange with rare earths and a subsequent Calcination are particularly effective activators for cracking catalysts. However, it is often observed that faujasites laden with rare earths, when added to cracking catalysts, s; ur formation of proportionately large amounts of coke and the formation of undesired "dry gas", i.e. a mixture of hydrogen, Methane, ethane, ethylene and acetylene lead.

The invention is therefore based on the object of an improved, thermally stable, rare earth element to produce synthetic faujasite, which is great as a promoter in hydrocarbon conversion catalysts possesses thermal stability, activity and selectivity.

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BATH ORIGINAL

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Another object of the invention is to provide an improved hydrocarbon cracking catalyst be proposed with zeolite as an activator, which selectively large amounts of desired petroleum and olefin products at the same time As little as possible formation of coke and Trcakengaaen supplies.

It has surprisingly been found that when you replace an alkali faujasite with a silicon dioxide: aluminum oxide ratio from about 2.5: 1 to 6.0: 1 with about 0.2 to 3% by weight (chromium ions, expressed as chromium oxide, and about 2 to 15% by weight of rare earth ions, expressed as trioxide a pH of about 2.0 to 4.0, followed by calcination at a temperature of about 316 to 81 ° C and subsequent washing to reduce the alkali oxide content to a value of about 0.5 to 4.0 wt. J an extremely stable and active zeolite is obtained which has essentially the same silica: alumina ratio like the faujasite used as the starting material.

Accordingly, the invention provides a synthetic faujasite with

a) a silica: alumina ratio of 2.5: 1 to 6.0: 1,

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BATH ORIGINAL

b) an RE ion content, expressed as RE ₂ O ₅ , of 2 to 15 wt. i, and

c) a chromium ion content, expressed as Cr ₃ O ,, of 0.2 to 3.0 wt

The novel zeolites can be amorphous inorganic matrix materials, for example silica, alumina, silica / alumina, clay, and mixtures thereof in amounts of about 5 to 50 wt.% Of zeolite, based on the final product, combine, said extremely effective hydrocarbon conversion catalysts are obtained.

The invention also relates to a method for producing a synthetic faujasite, which thereby is marked that one

a) at a pH of 2 to Ί a synthetic one Alkali faujasite with a silicon dioxide: aluminum oxide ratio of 2.5: 1 to 6.0: 1 an ion exchange with combined or separate aqueous Subjects to solutions of a chromium salt and an SE salt and

b) calcining the product obtained in step a) at a tempera ture from 516 to 816 ⁰ C.

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8AD ORJGiNAL

An alkali faujasite with a silicon dioxide: aluminum oxide ratio of 2.5: 1 to 6.0: 1 is generally found use as starting material. A zeolite X or zeolite Ϊ is preferably used as the starting material in the Sodium form (hereinafter referred to as NaX or NaY) is used. While in general the silicon dioxide The aluminum oxide ratio of the faujasite used as the starting material can be down to 2.5: 1, it is preferred that a faujasite having a silica: alumina ratio greater than 3: 1, preferably from 5: 1 to 6: 1 is used to the invention To manufacture products »

To obtain the desired exchanged faujasite the faujasite in the sodium form with separate or combined aqueous solutions of the rare earth salts and des Brought into contact with chromium salt. In general, the metal salts can be used in the form of chlorides, sulfates, Nitrates or other water-soluble compounds are present. However, rare earth chlorides and chromium chlorides are preferred.

The exchange solutions containing the metal ions for exchange with the sodium form of faujasite preferably contain about 0.1 to 0.4 mol / liter rare earth ions and about

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BATH ORIGINAL

0.01 to 0.2 mol / liter of chromium ions <> The pH of the Exchange solutions containing metal ions are adjusted to about 2 to 4, and preferably about 3 to 3.5. The pH value can be easily adjusted by adding a suitable mineral acid such as hydrochloric acid, sulfuric acid or nitric acid *

To achieve the desired degree of exchange, the sodium form of the zeolite is suspended in the exchange solution containing the metal ions for about 0.1 to 3 hours. The temperature of the solution is preferably maintained at about 80 to 105 ⁰ C. During the exchange with the metal ions, the alkali

/ on the metal content of the zeolite up to about 65 to 100 % of the original

/ the initially existing alkali metal, through rare earths,

Chromium and possibly protons is replaced.

Subsequent to the exchange with the solutions containing the metal ions, the faujasite loaded with the metal ions is for about 0.1 to 3 hours at a Calcined or heated at a temperature of about 316 to 81 ° C. Subsequent to this calcination, the faujasite is washed, preferably with an ammonium sulfate solution or with other ammonium salts, until the sodium content of the faujasite has a value of about 0.05 to

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1.0 wt% in terms of Na ₂ O _{4 is} decreased. This last step can be carried out either with the pure zeolite or already with the finished catalyst after the zeolite has combined with a matrix.

It turns out that the product according to the invention, exchanged with rare earths and chromium, has very good thermal and hydrothermal stability, as can be seen from this, that the surface is largely retained after treatment with steam at elevated temperatures. For example, the compositions according to the invention initially have a surface area of 750 to 950 m / g. According to a hydrothermal treatment, ie, a heating in a saturated steam atmosphere at a temperature in the range 760-871 ⁰ C _1, the product still possesses 70 to 80% of the original surface. Thus, when the products are subjected to a steam treatment at 732 ° C, the treatment conventionally used in the production of typical cracking catalysts containing faujasite, it is found that

that the products according to the invention after a 3 hour

Treatment still have a surface of 550 to 700 m / g.

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The stability of the compositions according to the invention performs very favorably in a comparison with faujasites, which are completely exchanged with SE cafions. In addition, the present products have a unusually high activity when used as Aktivatoicen for Find cracking catalysts use. The exact reason for the increased stability and catalytic activity the faujasite of the present invention is not fully elucidated, but it can be assumed that the small amount of Chromating the catalytic activity of the zeolite from Faujaalttyp noticeably increases. Furthermore, it can be assumed that when using the method according to the invention, both the chromium ions and the rare earth ions at such points be built into the faujasite structure where a maximum Effectiveness in terms of thermal stabilization and the increase in catalytic activity achieved will. The amount and arrangement of the significant number of acid units in the zeolite is likely to contribute contributes to its high catalytic activity. It was also found that when using the new method of working, i.e. by the metal ion exchange in the faujaoite a pH of around 2 to Ί, if only one very little extraction of alumina from the faujaaifc structure takes place. It therefore shows that the Products according to the invention have the same silica: alumina ratio as those for manufacture

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Alkali faujasites used for these products »

To produce catalysts from the faujasites according to the invention, conventional working methods for producing catalysts are used o For example, the present faujasites can be added to a conventional cracking catalyst, which consists of 25 to 50 % clay and 75 to 50 % silicon dioxide / aluminum oxide, by mixing the faujasite with the Catalyst ingredients mixed during any stage of catalyst preparation. Typical catalyst matrix components which are suitable for producing the catalysts include silicon dioxide, aluminum oxide, silicon dioxide / aluminum oxide, clay and mixtures thereof.

£ 8 has been found to be favorable that the use of a synthetic amorphous silicon dioxide / aluminum oxide for the preparation of the catalyst is of the alumina content of the mixture about 13 to 40 wt.%. When using clay as an additive, the desired results are obtained when using about 20 to 50% by weight of clay, based on the total composition of the catalyst. In general, it is found that when the present novel faujasites are used as activators, about 5 to 50 percent of the activator should be added to the catalyst composition.

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In a typical procedure for preparing the catalyst composition, an aqueous sodium silicate solution is first mixed with a mineral acid or carbon dioxide to produce a silica slurry gelled. The silica slurry can then be combined with an aluminum salt such as aluminum sulfate be combined such a ratio that the mixture the

^ has the desired aluminum oxide content. The silica / alumina slurry can then with the present novel paujasite are combined as an activator, whereupon, if desired, clay in the appropriate amount is added. The slurry is then filtered and washed to remove soluble impurities such as sodium and sulfate ions. Finally, the catalyst composition can be spray dried or pelletized and further washed and / or another one to remove residual sodium ions

"Are subjected to ion exchange.

The catalysts prepared as activator using the novel Paujasits prove to be particularly effective for the catalytic cracking of hydrocarbons, in which a Schweröleinsatysprodukt is subjected at a temperature of 127-538 ⁰ C cracking conditions. It turns out that the present

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Catalyst selectively delivers substantial yields of gasoline and olefins, while only small amounts of undesirable by-products such as coke and dry gases are formed. The present catalyst largely retains at its ursprünglich® crystallinity and surface when both catalytic cracking conditions and the even harsher regeneration conditions is subjected as in which the carbon on the surface of the catalyst at temperatures of 927-982 ⁰ C in the presence j burned off steam v / ird.

The following examples are intended to provide a more detailed explanation of the invention.

example 1

A number of rare earth and chromium-containing faujasifct-type zeolites were prepared with different contents of RE and chromium ions, so that the following compositions A, B, C, D and E were obtained.

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A. 100 g (dry basis) of a commercially available NaY zeolite with a silica / alumina ratio of about 5.2: 1 were slurried in 150 ml of water. 9.2 g of chromium chloride (CrCl, · 6Η ₂ Ο) were dissolved separately in 200 ml of water and treated with 46 ml of a commercially available solution containing 60% by weight of rare earth chlorides. The aqueous zeolite slurry produced was mixed with the chloride solution while stirring. The mixture formed had a pH of 3 »5. The mixture was ^{heated to 90 °} C. and kept at this temperature for 45 minutes with stirring. The exchanged zeolite was then filtered off, washed free of chloride and ^{dried at 104 °} C. for 1 hour. The product obtained, a greenish colored filter cake, was calcined for 3 hours at 538 ° C. and finally treated twice with an ammonium sulfate solution. The first treatment was carried out with 100 ml of a 10% aqueous ammonium sulfate solution by heating at boiling temperature for one hour. The composition and the thermal stability of this product (sample A) are given in Table I. It was observed that part of the chromium ions in the zeolite was eluted upon subsequent treatment with an aqueous ammonium sulfate solution.

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B. The procedure of paragraph A was repeated except that 23 »2 g of chromium chloride were used to prepare the exchange solution. The pH of the zeolite / metal chloride mixture was determined with dilute hydrochloric acid before Ion exchange set to 3 »5. The composition and the thermal stability of the product (Sample B) are also given in Table I.

G. The procedure in paragraph A was repeated, with however, the exchange solution was made with 4.64 g of chromium chloride. The pH of the exchange mixture was adjusted to 3.5 by adding hydrochloric acid before the start of the exchange. The composition as well as the thermal Stability of this material (sample C) can be found in Table I.

D. An exchange solution was prepared by dissolving 2.33 g of chromium chloride in 150 ml of water and then adding 11.5 ml of a 60% RE chloride solution. 25 g (dry basis) of a sodium molecular sieve partially exchanged with ammonia with an Na ₂ u content of 2.4 % and a silicon dioxide: aluminum oxide ratio of about 5.2: 1 was mixed with the metal chloride exchange solution. The slurry was heated to the boil for 45 minutes, filtered, washed free of chloride and

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dried and calcined at 538 ° C for hours. The calcined product was then used twice Amonium sulfate as described in Abeats A. The composition and the stability values for this Products (Sample O) are given in Table I.

E. The influence of the calcination conditions was investigated by taking a sample according to the procedure of paragraph A was produced, but the subsequent calcination was carried out under vacuum. The composition and the stability values for this product (sample E) can be found in the following table I.

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CD CO CO

O cn

Table I.

Composition and stability values for molecular sieves of type ϊ containing Cr and rare earth ions

thermal stability sample starting kalsinia % Na ₂ O % Na ₂ O % Cr ₂ O, % SE ₂ O, surface in m ² / g according to

material jungsbe- _VO r NHh- by NH, - by NH, - by NH, - _o ^{2 hours at} _ö txingunge _{Au> ttu} 3 _eh Austausdh AustausSh Austausdh 5 38 ° C 871 C

622

A. HaX air 2.98 0.24 1.14 7.05 838 B. NaY air 2.77 0.24 1.96 4.68 775 C. NaY air 2.90 0.20 0.87 8.86 733 D. (NH ₁ ,, Na) X air 1.44 0.31 2.00 16.02 613 E. NaY vacuum 2.98 0.36 1.50 7.88 727

549 I. μ »
VJl 641 t 98

675

TO CD

A comparison of the values for samples A and £ in the table above shows that the chromium content of the product calcined in air is slightly lower than that of sample E, which was calcined in vacuo, namely 1.14 versus 1.50 % Cr ₂ O,. The difference is due to a partial loss of chromium ions during the ammonium exchange. It is also noticeable that the RE content of the product calcined in air is somewhat lower. It should be noted that the low RE and chromium content of these zeolites makes it likely that a significant number of protons are present.

Example 2

The catalytic activity of the activators according to the invention was investigated by adding samples A, B and E in an amount of 10 or 15% by weight to a semi-synthetic matrix. For comparison, similar samples were used, which consisted of conventional calcined faujasites with an RE content of 18% by weight * (sample CREY). The samples were each added to a silicon dioxide / aluminum oxide / clay matrix which contained Ί0 % by weight of kaolin and 60% by weight of the synthetic silicon dioxide / aluminum oxide mixture, the latter consisting of 25% aluminum oxide and 75% by weight silicon dioxide. The samples were pelleted and one

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Subjected to standard microactivity cracking test. The results obtained are summarized in Table XI. In Table III there are ähnliehe results, which were obtained after the catalyst had been subjected to 8 hours prior to the test a steaming treatment at 732 ⁰ C.

The test conditions and the procedure can be found in detail in Ciapetta and Henderson, "Oil and Qas Journal", October 16, 1967. The food product was an oas oil (West Texas Devonian) which was discharged at a temperature of 27 ° C with a flow rate of 16 weight / hour.

Table II

Microactivity of catalysts with a Cr / SE molecular siob Y (fresh catalysts)

Investigated catalyst: mixture of 10 wt% sieve.

semi-synthetic matrix

Thermal pretreatment

of the activator: calcination for 3 hours

538 ° C

Use product: West Texas Devonian Gasul

Test conditions: 427 ⁰ C, throughput speed

16 wt./hour

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sample

CRET

ο co co

σ ro cn

Conversion to Vol. * 83.86 79.87 79, »1 79.83 I. NJ H ₂ in Qew.S 0.095 0.091 0.07 * 0.086 H" CD ^C l * ^C 2 * ⁿ ** * * * * 1.280 1.167 1,210 1.298 00 -P-
ro Dry gas in weight p 7.9 * 6.98 7.28 8.31 CD C "in Vol.S. 3, M 3.83 3.69 3, * 3 C- total in vol. % 11.05 9.61 10.09 11.67 C | / C ₅ total v / v 0.31 0.40 0.37 0.29 CJ in vol. * 1.46 1.59 1.28 1.32 Cj _{1 in} total in vol. * 20.66 17.58 17.83 21.05 Cj / Cj, total vol / vol 0.07 0.09 0.07 0.06 Cr 4 Gaeöl in vol. % 59.89 59.07 57.9 * 52.00 Ce ♦ GasOl / conversion product
⁵ vol / vol 0.71 0.7 * 0.73 0.65 Cj, ♦ QasCl in vol. % 80.55 76.65 75.76 73.26 C _k * GasOl / conversion product
* Vol./Vol. 0.96 0.96 0.95 0.92 Coke esp. Catalyst in Qew.JC 1.95 1.85 1.95 2, * 0 Coke esp. Feed product in Oev. 2 10.82 10.52 10.91 13.99 C ₅ ♦ Gas / Oil / Coke, Vol./Wt. 5.53 5.62 5.31 3.72 Random product / coke, Vol./Oew. 7.75 7.60 7.28 5.70

Table III below summarizes the results of a microactivity test in which the catalyst had been treated with 1.05 kg / cm of steam for 8 hours at 732 ° C. prior to the test. The input product was again West Texas Devonian Gasßl. A temperature of ^ 82 ⁰ C found at a throughput rate of 16 wt / hour. Use.

Table III

Microactivity of catalysts with a Cr / SE molecular sieve Y (after steam treatment)

Investigated catalyst; Thermal pretreatment:

Input product:
Test conditions:

Mixture of 10 or 15 wt.% Sieve with semi-synthetic matrix

Steam treatment for 8 hours at 732 ° C under 1.05 kg / cm ^{2 of steam}

West Texas Devonian Gaaöl Ί82 ^Ο (Σ, throughput rate 16 dew./h.

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sample

CREY

Ni O ΙΌ

Activator content in the catalyst 10 15th 15th 15th 15th I.
ro sator in wt.% 70.25 75.91 69.58 76.49 75.99 O Conversion into Vol. 2 0.052 0.039 0.028 0.024 0.023 I. H ₂ in weight * 0.708 1.006 0.852 0.048 1.491 ^C l * ^C 2 ^{in Qew} * 5.19 5.88 5.49 6.15 7.16 Dry gas in wt. X 6.23 6.57 6.39 6.43 6.58 C, in vol. * 7.36 8.04 7.66 8.44 9.41 C-, total in vol. % 0.85 0.82 0.83 0.76 0.70 C, / C, total v / v 1.24 3.63 4.34 3.79 2.54 C ₁ , in vol. * 10.97 10.96 11.51 11.99 12.13 C _{11 in} total in vol. % 0.39 0.33 0.38 0.32 0.21 Cj, / C ₁₁ total v / v 63.99 67.56 60.91 68.41 65.89 C ₅ ♦ Gas oil by volume? Cc ♦ gas oil / conversion 0.91 0.89 0.88 0.89 0.87 product vol. / vol. 74.95 78.53 72.42 80.40 78.02 C ₄ ♦ Gas oil in vol. T C ₁ , ♦ gas oil / conversion 1.07 1.03 1.04 1.05 1.03 product vol./vol. Coke or catalyst in 0.28 0.30 0.40 0.30 0.60 Weight} Coke or feedstock 1.64 1.76 2.31 1.74 3.47 . in wt% 39.01 38.44 26.38 39.24 18.27 Cc ♦ Qas oil / coke, vol./wt.

Conversion product / coke, vol./wt.

42.83 43.20

30.13

21.88

From the above Table II it can be seen that the catalysts according to the invention with a molecular sieve of the type Ϊ containing Cr and RE ions as an activator have high conversion values and very good selectivity for the formation of petroleum products from hydrocarbons with more than five carbon atoms, both for Zeolites calcined in air as well as under vacuum applies. The conversion is better or at least equally good as the conventional when using catalysts having CREY-activated M vator and the selectivity for petroleum fractions of hydrocarbons having more than five carbon atoms is 8 Vol.Jt higher than for the catalysts of the prior art. The yield of olefins is higher when using catalysts made from Cr-SE-Y-paujasite. It is also noticeable that the formation of coke is suppressed quite considerably in the case of the present catalysts.

It is clear from the results in Table III that the catalyst according to the invention has a markedly higher selectivity for gasoline than the conventional catalyst with a CREY activator. Furthermore, the yield of drying gas is significantly lower and the yield of olefins is higher. The ratios of petroleum fractions with hydrocarbons with more than 5 carbon atoms, see coke, and of conversion products, see coke, are twice as high as the corresponding values for the conventional catalyst.

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Claims (1)

Claims a) a silica / alumina ratio of 2.5: 1 to 6.0: 1, b) an RE xonen content, expressed as RE ₂ O ,, from 2 to 15 Qew.Jt, and c) a chromium ion content, expressed as Cr ₂ O ,, of 0.2 to 3.0 Qev.%. 2. Synthetic faujasite according to claim 1, characterized in that it, expressed as Na ₂ O, has a sodium content of 0.5 to 4 Qev.% . 3. Catalyst composition with a synthetic Faujasite in an inorganic amorphous matrix, characterized in that the faujasite is a chromium containing faujasite according to claims 1 or 2. 4. Process for the production of a synthetic faujasite, characterized in that one 109810/2025 a) a synthetic alkali faujasite with a Silica: alumina ratio of 2.5: 1 up to 6.0: 1 with a pH value of 2 to Ί simultaneously or successively an ion exchange with aqueous Subjects solutions of a chromium salt and an SE salt, and b) the product of the previous step is calcined at a temperature of 316 to 81 ° C. G 5. The method according to claim 4, characterized in that that the ion exchange within 0.1 to 3 hours. 6. The method according to claims 4 or 5, characterized in that the pH of the aqueous solutions brings it to 3 to 3.5. 7 · Process according to claims 4 to 6, characterized by * * draws that the ion exchange is carried out at a temperature of 80 to 105 ° C. 109810/2025 2Ü42730 8. The method according to claims * i b5a 7j characterized in that the calcined product is washed to reduce the alkali metal content to 0.05 "-" iß 3.0 wt, J5, expressed as M, 0, where M is an alkali metal, too
humiliate. 9. The method according to claim 8, characterized in that the calcined product with ammonium sulfate solution washes c coll: wy 109810/2025 BAD ORlQi _NAL