DE2144727B2 - Process for reactivating a supported catalyst containing platinum, lead and a third metal component - Google Patents

Description

3 4

exploited a method for reactivating a catalyst containing carbon, platinum and lead

■ Hydrogen conversion is used.

sators to make accessible, in which the deposited The catalysts that the carbon according to the invention are subject to driving for a short time at low temperatures, platinum and lead are durable Can be burned, so that in economic 5-stopping catalysts, the at least a third contain a good regeneration of the catalysis component, such as lithium, sodium, potassium, sators is reached. Rubidium, cesium, copper, silver, gold, beryllium,

It has been found that this task can be achieved by magnesium, strontium, barium, zinc, cadmium,

can be resolved that the regeneration under add-mercury, yttrium, boron, thallium, titanium, zircon,

conduct of oxygen in two different stages io germanium, tin, vanadium, tantalum, phosphorus, anti-

at different temperatures and different, bismuth, chromium, molybdenum, tungsten, manganese,

borrowed oxygen content of the oxygen-containing gas rhenium, iron, cobalt, nickel, ruthenium, rhodium

is carried out. dium, palladium, osmium, iridium, thorium, uranium

The invention thus relates to a method and the like.

to reactivate a supported catalyst used for hydrocarbon conversion, the platinum content is 0.01 to 3 percent by weight, the 0.01 percent and the lead content 0.01 to 5 percent by weight of platinum, 0.01 to 5 percent by weight, based on the weight of the catalyst, cent lead and contains a third component and a The third component is added in a proportion of 0.01 weight ratio of lead to platinum of 0.1 to 3 to 3 percent by weight. Has preferred contents, which is characterized in that in 20, however, 0.1 to 1.0 percent by weight of platinum, 0, i) 5 of a first stage for 2 to 5 hours at 300 to 3 percent by weight of lead and 0.05 to 1 weight-45O ⁰ C a 0.5 to 5 volume percent oxygen containing percent of the third component. In addition to the tendes gas and then in a second stage during the specified percentages, the ratio Pb / Pt 1 to 3 hours at 450 to 550 ^c C, a 5 percent by volume, is of important importance. Namely, when the ratio or more of oxygen-containing gas passes through the reactivating catalyst to 25 of Pb'Pt exceeds a predetermined value. Pb exerts a permanent poisoning effect on Pt

An important feature of the inventive method. and the ratio Pb / Pt is therefore 0.1 to 3

In driving, the burning of deposited coal (as a weight ratio) is limited. It is preferred

substance at a temperature below 450 ° C for a short time. as a platinum component a halogen-containing

Duration. so as not to use the high temperature bond.

Promote firing or sintering of the active species. As the carrier material, alumina, Si-The reason that the treatment at this low-temperature silicon dioxide, silicon dioxide-aluminum oxide and the like is preferred for such a short time. An oxide is suitable as a starting material; it can be used for a period of time; hydroxide or hydrate is probably one of the materials mentioned can.
Material and for burning that material. When treating the catalyst with a gas containing oxygen at 450 to 550 ° C in the final stage, an initial process is carried out to achieve a very oxygen concentration, a concentration of little amount of remaining deposited 40 less than 5 ⁰ O preferred. Preferably, this carbonaceous material is burned, and the concentration is completed depending on the amount of waste within the shortest possible time. The stored carbon, the treatment temperature, treatment at 450 to 550 ° C in the final stage of the flow rate of the treatment gas, is also advantageous if it is regulated under a pressure of the amount of the catalyst so that the Temvon 1 to 20 kg / cm ^{2 of} a Gas flow carried out 45 temperature of the catalyst layer is not increased because the burning of carbon-containing. In a very effective embodiment, the material is conveyed. If, however, the first stage of the process according to the invention is carried out with an acid under pressure, the linear substance concentration of 0.5 to 1.0 "" at the beginning of the velocity of the gas is lower, as a result of which reaction easily begins and this concentration occurs overheated areas, which naturally unfavorable- 50 gradually increased to 5 °,
is liable. The initial reactivation temperature is in

The supply of halogen or a halogen range from 300 to 450 ° C, preferably in the range

compound in the method according to the invention from 400 to 450 ° C. An effective treatment time

can be completed within a short period of time. is up to 5 hours and is in particular in

It is sufficient if halogen as a raw material 55 ranges from 3 to 5 hours. It is not preferred

used oil or a reactivating gas to increase the initial treatment temperature

mixture at the end of the reaction period and to extend the reaction time, because both factors

is mixed. speed up long-term activity

The reason for the quick effect, which increase through the reduction.

The addition of halogen is achieved within the range of 60 It is then necessary to adjust the oxygen concentration

holds lead in addition to platinum in the process according to the invention in the later treatment stage with an oxygen

applied catalytic system, and it is con- taining gas to a value greater than 5% too

assume that the lead component is effective in bringing in. Air can also be used for this,

that of halogen. In some cases, pure oxygen can also be used.

The essence of the invention is that the 55 are turned. It is advantageous that a temperature

Oxygen reactivation stage and the chlorine reaction in the range from 500 to 550 ° C and a treatment

the fourth stage is carried out effectively, it lasts up to 3 hours,

the. adding the characteristic property of the supply of halogen is then applied

5 6

If the reactivation is carried out with an oxygen containing shorter duration, the reacting gas is difficult or, if desired, activation with less effort and reduced the reactivation with an oxygen containing cost. The process according to the invention is technically more efficient to undertake gas. The temperature is advantageous because the reactivation is carried out in as short a time as temperature and the duration of the halogen supply stage 5 is carried out within 8 hours and because this can have the same values as in the stage of changing the catalyst in the reactor without treatment Oxygen containing gas. is required.
So the supply of halogen during the pre-. ,
Initially the treatment with an oxygen contained B e ι s ρ ι e ι
The gas can be carried out, and the calogen can be in the form of powdered aluminum oxide (γ- aluminum oxide) in the presence or absence of oxygen - with a purity of 99.9% it would be a grain. According to another embodiment, it is granulated in size of 2 ml and then ^{burned for 5 hours at also possible a halogen or a halogen compound 650 0} C to produce a carrier,
Manure in dissolved form in the with the catalyst This was introduced in an aqueous solution of Chlorobehandelte A "cgangsmaterial before the 15 platinum acid, dipped lead nitrate and uranyl nitrate, is terminated to the reaction. To evaporated a halogen or a dryness, and 3 hours at 55O ⁰ C ge-halogen compound effective at a catalytic burns. In this case, a catalyst has to bind the composite system without loss, is preferred, the settlement (0.5% Pt - 0.5% Pb - 0.5% U) / Al ₂ Keep O ₃ supply of halogen or halogen compound in.

the later stage of the oxygen treatment in the anao Using the catalyst produced in this way

After the step of treatment with an acidifier, a reforming process was carried out for 100 hours.

make substance-containing gas. the under the following reaction conditions

The following are carried out as halogen or halogen compounds: reaction ^{temperature 500 °} C., reaction pressure

molecular halogen, hydrogen halide or a 10 kg / cm ² , ratio of H ₂ to gasoline or naphtha 5.0

Fluorine, Chlorine, 25 Hydrocarbon Compound, and Liquid Hour R-.aUL. Velocity (LHSV)

Used bromine or iodine. The amount of trains- 2.0 h ^-1 .

led halogen is preferably in the range of After the reaction, the catalyst was

0.1 to 10 percent by weight halogen, based on the gender method reactivated:

Weight of the catalyst. In cases in which mild Catalysts were selected one after the other.

Reaction conditions are applied, or in 30 rend 3 hours at 400 ⁰ C 1% oxygen containing

Cases in which the reactivation takes place at a point in time of gaseous nitrogen and 3 hours at 520 ⁰ C air

is carried out on which the activity of the catalyst is directed. After the described reaction and the

sators is not so much decreased, also that reactivation had been repeated 35 times

The addition of halogen is not always necessary. during 3 hours at 520 ⁰ C 1,1,2-trichloroethane is formed

The reaction in which the air that reacts according to the invention passes through in the final stage of reactivation.

fourth catalysts are used, the diversion. The amount of chlorine supplied was

Conversion of hydrocarbons, such as hydro- 1.5%.

cracking, dehydrogenation, isomerization, dehydrogenation Then the sequence of reaction and reactive cyclization, dealkylation, reforming and similar carbonization with oxygen was repeated 35 times and the reactive hydrogen conversions. The 40 to be used are activated by adding 1,1,2-trichlorohydrocarbons again and consist mainly of carbon ethane. The reactivation effect on hydrogen with a boiling point in the range of this point in time had the following value:
from 40 to 250 ° C. Industrially advantageous raw materials are light gasoline, heavy gasoline, kerosene, gas oil. Results of the reaction
and the like. The reaction conditions here can be a catalyst aromatics yield reaction ^{temperature of 300 to 650 °} C., in particular (percent by weight)

430 to 580 ° C, a reaction pressure of 1 to 50 kg / cm ² , Before reactivation (fresh) 69.1

in particular 1 to 20 kg / cm ² , a ratio of after 10 repetitions of the sequence of
Hydrogen to hydrocarbons from 0.5 to 15, reaction and reactivation (acidic preferably 2 to 10, and a liquid hour 50 substance process) 66.5

Space velocity from 0.25 to 10 h ^-1 applied after 20 repetitions of the sequence of

will. Reaction and reactivation (acid

For the method according to the invention, it is characteristic substance process) 64.2

drawing that reactivation at low tempe- After 35 repetitions of the sequence of

temperature and is carried out for a shorter period, 55 reaction and reactivation (acid

by the characteristic feature of the platinum and substance process) 60.3

Lead-containing catalyst is exploited. After reactivation (oxygen-ha-

advantages are achieved that lied with other catalysts process) 70.1

cannot be achieved. After 35 repetitions of the sequence of

according to procedures, the service life 60 reaction and reactivation (acidic

of the catalyst extended to such an extent as is the substance process) 61.2

up to now could not be observed if the after reactivation (oxygen-ha-

Result of reaction and reactivation repeated lying process) 69.9

will. It can also maintain high levels of activity. .
can be obtained, and therefore aromatics and 65 B e 1 s ρ 1 e 1 2
High octane oils at lower cost and The same carrier material as in Example 1 was obtained in higher yield. Since the reaction is immersed in an aqueous solution of chloroplatinic acid, lead activation at a lower temperature and while chloride and potassium chloride are immersed to dryness

evaporated and ^{fired at 550 0} C for 5 hours. In doing so, it became a catalyst of the composition

(0.3% Pt - 0.3% Pb - 0.1% K) / A1 ₂ O ₃

obtain. Using the catalyst thus prepared reforming for 70 hours under the following conditions was performed: reaction temperature 510 ⁰ C, reaction pressure 15 kg / cm ^2, ratio of hydrogen to gasoline 7.0, and liquid hourly space velocity (LHSV) 3.0 hr ^'1.

Then, a 1.0% oxygen were containing nitrogen stream for 3 hours at 42O ⁰ C and a 5.0% oxygen-containing nitrogen stream is passed for 3 hours at 520 ° C after the reaction by the catalyst in succession.

After the specified sequence of reaction and reactivation had been repeated 35 times, became Gaseous nitrogen containing 1,2-dichloroethane passed through the catalyst for 2 hours at 520 ° C. in the final stage of the reactivation. The ao The amount of chlorine supplied was 5.0%. The total aromatics yields achieved by using of the fresh catalyst (before reactivation), of the catalyst after 35 repetitions of the reaction and reactivation (oxygen process) and the catalyst after reactivation with the aid of Chlorine process were 68.7%, 61.4% and 67.7%, respectively.

Example 3

30th

The same carrier material as in Example 1 was in an aqueous solution of chloroplatinic acid, lead nitrate and cadmium nitrate, evaporated to dryness and calcined at 550 ° C for 5 hours. Included became a catalyst of the composition

(0.5% Pt - 0.4% Pb - 0.1% CdVAl ₂ O ₃

obtain. Using the catalyst prepared in this way, the reforming was carried out for 100 hours under the following conditions: reaction temperature 500 ° C., reaction ^{pressure 10 kg / cm 2} , ratio of H ₂ to gasoline or naphtha 7.0 and liquid hourly space velocity (LHSV) 2.0 h ^{- 1st}

After the reaction, the catalyst were then successively a 2.0% oxygen-containing nitrogen stream is passed for 2 hours at 430 ⁰ C and air for 3 hours at 510 ° C. A stream of air containing 1,1,2-trichloroethane was then passed ^{through the catalyst at 510 °} C. for 3 hours, 0.5% of halogen being added.

The indicated sequence of reaction and reactivation was carried out 70 times. In the reaction the following results were achieved:

Catalyst aromatic exhaust

(Weight percent)

Before reactivating 69.5

After reactivating once, 70.5

After 20 reactivations 68.8

After 50 reactivations 71.2

After 70 reactivations 70.0

60

Example 4

Using 10 ml of the same catalyst as in Example 3, the sequence of the reaction and reactivation were repeated. The reaction was carried out for 100 hours at a temperature of 500 ° C., a pressure of 10 kg / cm ² , a liquid * hourly space velocity (LHSV ) of 2.0 and a ratio of hydrogen to gasoline of 7.0, while the reactivation was carried out by adding 1,1,2-trichloroethane to the gasoline supplied as raw material 1 hour before the end of the reaction, so that 0, 5 percent by weight of chlorine, based on the catalyst, were fed. A stream of nitrogen containing 2.0 percent by volume of oxygen was then passed through the catalyst at 430 ° C. for 2 hours, followed by a stream of air at 510 ° C. for 3 hours. The results of the reaction before and after reactivation showed the following values:

Catalyst aromatics yield

(Weight percent)

Before reactivating (fresh) 69.5

After reactivating once 68.2

After 20 reactivations 67.0

Comparative experiment 1

The reforming was conducted under the same conditions as in Example 1, except that the treatment was carried out in the initial stage for 5 hours at 500 ⁰ C and the treatment in the later stage for 5 hours at 580 ° C when reactivating the catalyst .

The following reaction results were achieved with this catalyst:

Catalyst aromatics yield

(Weight percent)

Before reactivating (fresh) 69.1

After 10 repetitions of reaction
and reactivation (oxygen process) 66.3

After 20 repetitions of reaction
and reactivation (oxygen process) 60.8

After 35 repetitions of reaction
and reactivation (oxygen process) 56.6

After reactivation (oxygen-halogen process) 66.4

After 35 repetitions of reaction
and reactivation (oxygen process) 51.3

After reactivation (oxygen-halogen process) 62.5

Comparative experiment 2

The reforming was carried out using the same catalyst and under the same conditions carried out as in Example 3, with the exception that when reactivating the catalyst Treatment in the first reactivation stage for 2 hours at 500 ° C and the treatment in the later stage was carried out for 3 hours at 580 ° C. The following reaction results were achieved:

Catalyst aromatics yield

(Weight percent)

Before reactivating 69.5

After reactivating once, 70.9

After 20 reactivations 67.3

After 50 reactivations 63.4

After 70 reactivations 58.2

Comparative experiment 3

The same support as in Example 1 was immersed in an aqueous solution of chloroplatinic acid, for

409544/340

9 10

Evaporated dry and 1 hour at 58O ⁰ C The following reaction results were achieved:

burns, a catalyst of the composition catalyst aromatics yield

0.5% Pt / Al ₂ O _{3 was} obtained. Using (weight percent)

of 10 ml of the catalyst prepared in this way, the before reactivation was 58.3

Sequence of reaction and reactivation among the 5 After reactivating once 60.2

same conditions as in example 3 again after 20 reactivations 53.0

get. After 50 reactivations 47.5

Claims (3)

1 2 application suggested. For example, the following claims are included: reactivation method for platinum-aluminum oxide catalysts or a third component 1. Process for reactivating a platinum alumina catalyst used for carbon tende, the hydrogen conversion 5 currently used extensively for reforming sators, the 0.01 to 3 weight percent platinum, 0.01 find, usually an oxygen reactivation to 5 Weight percent lead and a third compo- method and a halogen reactivation method contains component and a weight ratio of lead is applied. In the first-mentioned method, it is necessary to have platinum from 0.1 to 3, which is characterized by the use of an oxygen, that carbon deposited in a first io-holding gas is carried out at a high level for 2 to 5 hours at 300 to 450 ⁰ C temperature to burn for long duration. The a 0.5 to 5 volume percent oxygen-containing long-lasting treatment of a catalyst at gas and then the sintering of the active 1 to 3 hours at 450 to 550 ⁰ C in a second stage during high temperature promotes a 5 Volum- species and accelerated as a result, the rate the percent or more oxygen-containing gas 15 long-term deactivation. Namely when the exhaust passes through the catalyst to be reactivated. stored carbon, which is the cause of short-term 2. The method according to claim 1, characterized in that deactivation is considered to be removed, draws that one additionally contains a halogen or a phenomenon occurs that the growth of Halogen compound-containing gas occurs in a particle of the active species. It will be paid for Amount passed through the catalyst that 20 suppose that the cause of a phenomenon 0.1 to 10 weight percent halogen based on long-term deactivation, which is disadvantageous. To the Catalyst, are supplied. on the other hand, in cases where the oxygen 3. The method according to claim 1 or 2, characterized in that the reactivation method is not sufficient, a halogen indicates that the second stage of the reactivation method is used. This method of conversion for 1 to 3 hours at 450 to 25 is based on the addition of chlorine and the like to the active 55O ⁰ C under a pressure of 1 to 20 kg / cm ² species in order to effect an acidic function, as is carried out . Hydrocracking, isomerizing, cyclizing and the like Although these two methods described above are widely used, they lose industrially 30 began to use common catalysts theirs Activity and become unusable. Such a catalyst that has become ineffective must be subjected to an extraction The invention relates to a method of reaction to obtain the active ingredient, such as four of a platinum for hydrocarbon conversion, subjected to and again in a cata- applied supported catalyst, the 0.01 to 3 weight 35 lysator are transferred. The manufacturing cost percent platinum, 0.01 to 5 percent by weight lead and the catalyst and the cost of replacing the contains a third component and is a weight catalyst in an industrial device lead to platinum ratio of 0.1 to 3, the cause of an increase in production costs, its activity in a hydrocarbon conversion according to the invention has received particular attention treatment reaction has been reduced. 40 to the disadvantage of conventional reactivation As directed in the German Offenlegungsschrift 2 005 828 method of the catalyst. Explained by is, catalysts using platinum and lead have carried out extensive studies with a view to reacting or platinum, lead and a third component containment method for platinum and lead-containing catates, With numerous advantages over a conventional analyzer, a reactivation method has become more fun Platinum-aluminum oxide catalyst or a 45 den, through which a stable, long-lasting process-like Catalyst. They are economically advantageous. adhere to catalysts for the production of aromatic Die platinum and lead or platinum, lead and a third Compounds, for example benzene, toluene, xylene, component-containing catalysts, which according to Trimethylbenzene, a base material for gasoline, can be reactivated with the method according to the invention, high octane number, in particular a base material 50 have the advantage already mentioned that the Verminfür unleaded petrol, due to its high fluidity, its activity is very low. Even if one keits yield, aromatic yield, the achieved high conventional oxygen reactivation method or a Cctane value, the hydrogen yield and its halogen reactivation method is used, wrestling rate of activity reduction. can of course be expected to be catalytic There has also already been a process for dehydration which is longer than that of a platinum catalyst, tion of dehydrogenatable alkanes, cycloalkanes or which does not contain lead. In fact later show an-arylalkanes Comparative examples given in the presence of a catalyst show that these catalysts beaten, who have a precious metal on a carrier and have a longer lifespan. Lose anyway Another metal, including lead, gives rise to their activity, albeit to a lesser extent can hold (German Offenlegungsschrift 2 026 121). 60 can no longer be used. If natural this Catalyst can be generated by conventional processes, the process under milder reaction conditions as is carried out by treating the catalyst, the activity is reversed with steam-thinned air with a certain reduction. Current aspirations th oxygen content. however, there are increasingly stringent requirements In the past, numerous researches were carried out on the quality of the product, for example work with regard to a reactivation- a higher aromatic concentration, a higher Oc- method for reforming catalysts carried out, and tan value. different processes have been used for the industrial The invention is therefore based on the object