DE2141286C3 - Use of alkali polyaluminates as catalysts for side reactions in the catalytic cracking of hydrocarbons - Google Patents

Description

3 4

washed and heated to a temperature of 650 ° C

warms. Then the treated Ge e ι s ρ ι e

mixture for the preparation of a catalyst tablet-2,3-dimethylbutene-2 was made using

animals. The composition of the catalyst developed /? "- Al ₂ O ₃ at a reaction temperature ^{of 230 0 C}

spoke the ratio 5 and a gas space velocity of 1 vol / vol / h

MgO: / T-Al ₄ O ₃ : Fe ₁ O ₃ : CuO = 40: 32.8: 18.2: 4.5. isorized.

The dehydration of butene using result:
of the catalyst produced in this way at a reaction temperature of 650 "C, a gas space velocity of olefin type volume percent

speed of 800 (vol / vol / h) and a water vapor '

Butene ratio of 15 (ks / l), resulted in the following qh qh CH = CH 0

^RESULTS: "CH ₃ -CH = CH-CH ₃ 25

Conversion (mole percent) 63.2

Selectivity (mole percent) 80 ¹⁵ ( ^CH 3) _ä <~ - <~ H ₂ 20

Yield (percent) 50.6 (CH ₃ ) ₂ C = CH - CH ₃ 50

Herein (CH ₃ ) _{2 means} C - C (CH ₃ ), 5

Conversion = butadiene produced (mol) _{] (χ) ao Furthermore, the isomer jation of} 2,3-dimethyl-

converted butadiene (mol) butene-2 under the same conditions as above,

. , .. .. oii- · - but with activated clay as contact through-

Yield = conversion selectivity. _{guided> wove the product of the following combination} -

If, on the other hand, a commercial catalyst was obtained from exposure:

72.4% MgO, 18.4% Fe ₈ O ₃ , 4.6% Cuo and 4.6% K ₂ O as

used under the same conditions as before

The results were as follows: Olefin type% by volume

Conversion (mole percent) 42

Selectivity (mole percent) 70 CH ₃ - CH ₂ - CH = CH ₁ 0

Yield (percent) 29.4 ³ ° _{CHj_CH = CH_CH3 237}

In this case one regeneration was for each (CH ₃ ) ₂ C = CH ₂ 18.9

30-minute cycle is required, while

Use of the catalyst according to the invention no (CH ₃ ) ₂ C = CH - CH ₃ 4 /, 5

There was a need for regeneration and even 35 (CH ₃ J ₂ C = C (CH ₃ ) ₂ 9.9

after 20 hours of continuous operation none

Change in the butadiene yield occurred and B e i s o i e 1 4

even after using the catalyst for 2000 hours

no decrease in catalyst activity observed. To a mixed solution of copper nitrate and

would. 40 iron nitrate (trivalent or bivalent) was

^{Example 2} 0-Al ₂ O ₃ (K ₂ O-11 Al ₂ O ₃ )

/ 3'-Ai ₂ O ₃ (K ₂ O-7-8 Al ₂ O ₃ ) powder was pelletized

and for the production of a carrier added at a temperature as a fine powder and stirred

Fired at 1450 ° C. The carrier obtained was mixed with 45. Calcium carbonate was converted into hexachloroplatinic acid solution for precipitation soaked and joined on one. The resulting precipitate was filtered off, heated to a temperature of about 600 ° C., washed and dried to obtain a catalyst sator with the ratio composition

Pt: / 3'-Al ₂ O ₃ = 1.0: 99.0 ₅₀ Fe: Cu: / S-Al ₂ O ₃ = 100: 5: 50

to create.

Using the catalyst thus obtained to produce.

and a starting material with a ratio The catalyst thus obtained was in the Fischer-

Oxygen to ammonia to methane Tropsch synthesis at a reaction pressure of

= 1 50 · 1 00 · 1 08 55 10 kg / cm ² , a reaction temperature of 200 to 230 ° C, a space velocity of 400 liters

the dehydrogenation and condensation reaction gas / kg Fe and H ₂ / CO = 0.85 was used. The following results were obtained from butane-ammonia at a reaction temperature:
carried out at 1000 ° C. The yield of hydrogen cyanide

HCN 60 yield (g / m ³ CO + H ₂ ):
κ o, _{o /} (HCN mol / NH ₃ mol) · 100 150 g liquid substance and

was 92 / _0th . 15 g of gaseous hydrocarbon

Then the reaction was carried out under the same conditions repeated as before, with a porcelain gasoline (<200 ° C) 55%

Reaction tube was used, the inside of which was 65 (olefin content 30%)

with a catalyst made of 70% platinum and 30% active agent oil (200 to 300 ⁰ C) 30%

fourth clay was lined. The gas oil reached (300 to 400 ° C) 10%

HCN yield was 90%. heavier oils (> 400 ° C) 5%

The catalyst used in the aforementioned reaction could run for about 2 years without regeneration will.

A Fischer-Tropsch synthesis was used a catalyst of the composition

Fe: Cu: Al ₁ O ₃ : K ₁ O: SiO ₁ = 100: 25: 9: 2: 25

carried out under the same conditions as before. The product obtained had the following composition:

Gasoline (<200 ° C) 71 °;

Medium oil (200 to 320 ⁰ C) 20%

Soft wax (320 to 46O ⁰ C)

Hard wax (> 460 ° C) 9%

After many years of operation, so much carbon had deposited on the surface of the catalytic converter that that its activity was decreased and a regeneration treatment of the catalyst is found proved necessary.

Example 5

In a chromium nitrate solution it was
/ 3 "-Al ₁ O ₃ (K ₂ O · 5-6Al ₁ O ₃ )

added in the form of fine powder, and then the whole was added with stirring to precipitate K ₁ CO ₃ , the resulting precipitate was filtered off, washed, dried and then to produce a catalyst with a ratio

Cr: 0'-Al ₁ O ₃ = 1: 9
tabletted.

Using the catalyst thus prepared, the cyclization of 2-Äthylhexen-l at a space velocity of 0.11 v / v was / h and a reaction temperature of ⁰ C SOO performed. The following results were obtained:

Liquid yield (%) 48

Aromatics (%) 91.0

Olefins (%) 7.2

Paraffins (%) 1.8

Furthermore, a cyclization reaction of 2-ethylhexene-1 was carried out under the same conditions as above, but using a catalyst of the composition Cr: V-Al ₁ O ₃ = 1: 9, the following results being obtained:

Yield of liquid (%) 50

Aromatics (%) 89

Olefins (%) 8.6

Paraffins (%) 2.4

Example 6

In a mixed solution of nickel salt, cobalt salt and molybdenum salt was made

/ 3 "-Al ₅ O ₃ (K ₂ O · 5-6Al ₂ O ₃ )

entered in the form of a fine powder and mixed. The whole was then admixed with K ₅ CO ₃ with stirring for precipitation. The resulting precipitate was filtered off, washed and dried, and then to produce a catalyst having the composition

Nickel to cobalt to molybdenum to / T-Al ₂ O ₃

= 2 .. ~. ο. OO

o selected.

The results of direct hydrodesulfurization using the catalyst so prepared were as follows:

Process conditions:

Reaction ^{temperature (0} C) 350 to 370

Reaction pressure (kg / cm ² ) 40

Space velocity (vol / vol / h) .. 2
_o H ₂ ZOl (m ³ / l) 2 to 2.5

In front

To

Treatment treatment

specific weight 0.9296 0.9139 (15 ° C / 4 ° C) 30 pour point (° C) + 10.0 - Remaining carbon content 6.74 - (Weight percent) Sulfur content 1.90 0.178 (Weight percent) Desulfurization (%) - 91

After continuous operation for 2000 hours, there was hardly any deposition of carbon observed the catalyst and impairment of the catalytic activity.

The direct hydrodesulfurization was carried out with the aid of a catalyst of the composition
45

Mo: Co: -Al ₂ O ₃ = 3.5.6: 3.0: 91.4

performed under the following conditions. The following results were obtained:

Conditions:

Reaction ^{temperature (0} C) 350

Reaction pressure (kg / cm ² ) 40

Space velocity (vol / vol / h) 1

H ₂ / oil (m ^3/1 ) 1

Results:

Sulfur content 0.29%

Desulfurization 85%

Claims (2)

ίο 2 • ^ is reduced, which in turn usually requires regeneration of the catalyst by burning off the deposited carbon. 1. The use of a catalyst completely or However, as the regeneration de · »catalyst to partially deposited carbon is used from at least one of Aikalipoly- 5, 2:11 remove occurs aluminate / 3 alumina (Me ₁ O · Al 11 O _{t s} ), with it slightly an abnormal temperature increase in the / S'-aluminum oxide (Me ₁ O 7-8Al ₁ O ₃ ) and / T-AIu catalyst layer, which not only leads to an impairment of the aluminum oxide (Me ₂ O 5- 6Al ₁ O ₃ ) (Me = Na or K) impairment of the catalyst activity, but also as well as at least one element from group VIII leads to a reduction in the performance of the reactor, the periodic table, chromium, tungsten, molybdenum _lo In addition, the regeneration treatment is very difficult Copper or its salts, for which Hy- ständlich. dration, dehydrogenation, isomerization, cycli- As already mentioned, the alkali polyaluminates inhibit sation, condensation, hydrodesulfurization or by the alkali metals they contain Fischer-Tropsch synthesis reaction of carbon - the deposition of carbon, and the speed hydrogen. 15 the rate of decomposition and volatilization of the alkali 2. Use of a single metal catalyst is very low. The alkali polyaluminates refractory support and at least 1 % alkali poly- β - aluminum oxide (MeJ ₁ O 11 Al ₂ O ₃ ), ß '- aluminum aluminate (calculated as Na ₁ O and / or K ₁ O) for oxide (Me ₁ O 7 -8Al _s O ₃ ) and ^ "aluminum oxide catalytic ^ conversions of hydrocarbons (Me ₁ O · 5-6AIjO ₃ ) (Me == Na or K) are characterized according to claim 1. ao that the speed of the Ak- Reduction in the activity of the catalyst associated with alkali evaporation and a disadvantage of conventional catalysts is low and that the life of the catalyst is quite long. * 5 It was also found that the alkali polyaluminates The invention relates to the use of a catalyst excellent selectivities for each reaction lysators for side reactions of the catalytic crack can be borrowed by using them as a carrier kung of hydrocarbons, as in claim 1 suitable catalyst substance, z. B. chromium, tungsten, and in addition to catalytic cracking molybdenum, iron, cobalt, nickel, copper, platinum, run off of hydrocarbons. 30 palladium, iridium, ruthenium, P.hodium and os- In the German Offenlegungsschrift 20 20 981 mium, in the form of an element, a compound or has been described in detail using a mixture. Hence, when using Alkali polyaluminates for the catalytic cracking of the alkali polyaluminates as catalysts none or steam reforming of hydrocarbons - need to regenerate the catalysts, materials because of the selectivity of the catalyst for the 35 approximately - as mentioned above - deposited carbon oxidation reaction To burn out ethylene in high yield. The reactor output can also be maintained and, furthermore, the deposition of carbon can be increased. the catalyst can be prevented, so that the invention is accordingly characterized a gas with a satisfactory composition, such as net, that for hydrogenation, dehydrogenation, isomeric Town gas with a high calorific value can be obtained. 40 ization, cyclization, condensation, hydrosulfuri- These are alkali polyaluminates of the sation or Fischer-Tropsch synthesis reaction of Group β - alumina (R ₁ O 11 Al ₁ O ₃ ), ß ' - alumina hydrocarbons a catalyst is used, (RjO -7-8 Al ₁ O ₃ ) and ß " - alumina (R ₁ O · 5-6Al ₁ O ₃ ), which consists entirely or partially of at least one of the where R = Na or K. Alkali polyaluminates It has now been found that when using a 45 Catalyst, which is wholly or partially composed of at least / 3-aluminum oxide (Me ₁ O · HAl ₁ O ₃ ), one of the alkali polyaluminates β - aluminum oxide ^ '- aluminum oxide (Me ₁ O · 7-8Al ₁ O ₃ ) and (Me ₁ O · HAl ₁ O ₃ ), ß ' - aluminum oxide (Me ₁ O- / 3 "-AlUmInJUmOXId (Me ₂ OS-EiAl ₁ O ₃ )
7 - 8Al ₁ O ₃ ) and ß " - aluminum oxide (Me ₂ O · 5-6Al ₂ O ₃ ) (Me = Na or Ka) as well as at least 50 (Me = Na or K) as well as at least one element an element from group VIII of the periodic table, from group VIII of the periodic table, chromium, Wolf-chromium, tungsten, Molybdenum and copper or their ram, molybdenum and copper or their salts. Salts consists, for the hydrogenation, dehydrogenation, iso- Preferably, for the catalytic conversion merization, cyclization, condensation, hydrodesul- of hydrocarbons, a catalyst according to the hardening or Fischer-Tropsch synthesis reaction of 55 is used, which consists of a! Refractory Carrier hydrocarbons the deposition of carbon and at least 1% _{alkali polyaluminate (as Na 1} O substance on the catalyst can be prevented, and / or K ₂ O is calculated),
and these catalysts and supported catalysts from The invention is to have preferred selectivity in the following with reference to the exemplary embodiments and test results mentioned in claim 1. 60 explained in more detail. Because carbon easily changes in the course of the process
Deposits on a catalyst are deposited namely, in these side reactions, the conditions for an aqueous solution of ferric sulfate became such as the reaction temperature and the ratio of the components, a copper sulfate solution was then added Ingredients very strictly controlled to the carbons 65/3 "-Al ₂ O ₃ (K ₂ O · 5-6Al ₈ O ₃ ) and MgO in the form of a to prevent material separation. There is, however, little powder added to the solution, and this rig, the carbon deposition completely was precipitated by the addition of ammonia. the Prevent, which is why the activity of the catalyst was reduced precipitate was filtered off with water