DE2144727C3 - Process for reactivating a supported catalyst containing platinum, lead and a third metal component - Google Patents

Description

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 tasters

percent platinum, 0.01 to 5 percent by weight lead and the catalyst and the cost of replacing de?

contains a third component and contains 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. By exc

is explained, have catalysts that are platinum unc! Lead extended investigations into reactivity

or platinum, lead and a third component containment method for platinum and lead containing kata

A reactivation method was found to have numerous advantages over a conventional analyzer

nellen platinum-aluminum oxide catalyst or a 45 den, through which a * stable, long-lasting process

similar 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, the nad Trimethylbenzene, a base material for gasoline, can be reactivated with the method according to the invention

high octane number, especially a base material have the advantage already mentioned that the Vermin

for unleaded gasoline, due to their high fluidity the activity is very low even when one

keits yield, aromatic yield, the achieved high conventional oxygen reactivation method or unites

Octane 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 method of dehydration life that is longer than that of a platinum catalyst

tion of dehydrogenatable alkanes, cycloalkanes or which does not contain lead. In fact show later

Arylalkanes in the presence of a catalyst given comparative examples that this catalyst

beaten, who have a precious metal on a carrier and have a longer lifespan. Still loses

Another metal, including lead, has its activity, albeit to a lesser extent, unc

can hold (German Offenlegungsschrift 2 026 121). 60 can no longer be used. If natural

This catalyst can be carried out by customary processes, the process under milder reaction conditions

are generated, as is carried out by treating the catalysis, so the activity will be

sators with steam-thinned air with a certain reduction lower. The present stress

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.

Various methods have been used for industrial purposes. The invention is therefore based on the object

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

Hydrogen conversion, carrier catalyst is used.

The catalysts that are subjected to the carbon according to the invention at mederer temperature within a short drive are platinum and lead can be burned permanently, so that in economic catalysts, the at least a third licher where »a_good regeneration of the catalyst contains components, 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, zirconium,

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. aiuxa, palladium, osmium, iridium, thorium, uranium

The invention thus relates to a method and the like

to reactivate a supported catalyst used for hydrocarbon 15 The content of platinum is 0.01 to 3 weight conversion, the 0.01 percent and the content of lead 0.01 to 5 weight percent platinum, 0.01 to 5 weight percent, 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 ao, however, 0.1 to 1.0 percent by weight of platinum, 0.05 of a first stage for 2 to 5 hours at 300 to 3 percent by weight of lead and 0.05 to 1 weight -450 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 is 1 to 3 hours at 450 to 55O ⁰ C, a 5 percent by volume of importance. Namely, when the ratio or more of oxygen-containing gas passes through the to as of Pb / Pt a predetermined value, the reactivating catalyst passes. Pb exerts a permanent poisoning effect on Pt

An important feature of the inventive method, and the Pb / Pt ratio 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 compound

Time 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 an ^{oxygen-containing gas, the treatment at 450 to 550 0} C in the final stage is initially carried out to achieve a very oxygen concentration, a concentration of little amount of remaining, deposited * o less than 5 %. 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 of the flow rate of the treatment gas, stage is also advantageous if it is regulated under a pressure of the amount of the catalyst so that the Temof 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. However, if 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, whereby reaction easily begins and this concentration occurs overheated areas, which of course unfavorable- 50 gradually increased to 5%, is liable. The subsequent reactivation temperature is in

The supply of halogen or a halogen range from 300 to 450 ⁰ C, preferably in the range

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

can be completed within a short period of time. takes up to 5 hours and is especially important in the

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 65 are turned. It is advantageous that a temperature Oxygen reactivation stage and the chlorine reaction in the range from 500 to 55O ⁰ C and a treatment

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

which by 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 reactivation gas is difficult or, if desired, activation with less effort and reduced the reactivation with an oxygen containing costs. The process according to the invention is technically more effective 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 stage of halogenate feed 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
Thus, the supply of halogen during the pre _R. · Ι ι
At the beginning of the treatment with an oxygen-containing B e ι s ρ ι e
The gas can be carried out, and the halogen can be xo Powdered aluminum oxide (y-aluminum oxide) in the presence or absence of oxygen - with a purity of 99.9% became one 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,
dung in dissolved form in the with the catalyst This was introduced into an aqueous solution of chloro-treated starting material before the platinic acid, lead nitrate and uranyl nitrate is dipped to the reaction. To a halogen or a dry evaporated and 3 hours at 550 ⁰ C ge-halogen compound effectively burns to a catalytic Here a catalyst was to bind the composite system without loss, is preferred the settlement (0.5% Pt - 0.5 % Pb - 0.5% U) / Al ₂ O ₃ keep the supply of halogen or halogen compound in place.

the later stage of the oxygen treatment in the an * o 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 *, ratio of H ₂ to gasoline or naphtha 5.0

Fluorine, Chlorine, AS Hydrocarbon Compound and Liquid Hourly Space Velocity (LHSV)

Used bromine or iodine. The amount of trains- 2.0h ^-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 time of gaseous nitrogen and 3 hours at 520 ° C in air

is carried out on which the activity of the catalyst is passed After the 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 which is reactive according to the invention passes through in the final stage of reactivation

fourth catalysts are used, the bypassed 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, dealalkyiation, reforms and similar carbonization with oxygen was repeated 35 times and the reactive hydrogen conversions. The 40 ti many to be used by adding 1,1,2-trichlorohydrocarbons again 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 ⁰ C. Industrial Vortel-like raw materials are light naphtha, heavy naphtha, kerosene, gas oil results of the reaction
and the like. The reaction conditions here can be a 45 Catalyst aromatic yield, reaction temperature of 300 to 650 ° C, in particular (percent by weight)

430-580 ° C, a reaction pressure of Ibis 50 kg / cm ⁴ , 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 ~ * applied after 20 repetitions of the sequence of

will. Reaction and reactivation (sour

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 reached. 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

so far could not be observed if the After reactivation (oxygen-Ha-

Result of reaction and reactivation repeated lying process) 69.9

will. In addition, a high level of activity can be maintained. .
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 ° 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 prepared in this way, the reforming was carried out for 70 hours under the following conditions: reaction temperature 510 ° C., reaction ^{pressure 15 kg / cm 8} , ratio of hydrogen to gasoline 7.0 and liquid hourly space velocity (LHSV) 3.0 h / to

Then, after the reaction by the catalyst, one containing 1.0% oxygen successively became Nitrogen flow for 3 hours at 420 ° C and a nitrogen flow containing 5.0% oxygen during 3 hours at 520 ° C passed.

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 »o 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 »5 catalyst after reactivation with the aid of the Chlorine process were 68.7%, 61.4% and 67.7%, respectively.

Example 3

30th

The same carrier material as in Example 1 was immersed in an aqueous solution of chloroplatinic acid, lead nitrate and cadmium nitrate, evaporated to dryness and ^{fired at 550 °} C. for 5 hours. In doing so, it became a catalyst of the composition

(0.5% Pt - 0.4% Pb - 0.1% Cd) / Al 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, successively a 2.0% oxygen was then passed through the catalyst-containing "nitrogen stream is passed for 2 hours at 430 ⁰ C and air for 3 hours at 510 ⁰ 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 aromatics yield

(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 reaction and reactivation was repeated. The reaction was carried out for 100 hours at a temperature of 500 ⁰ C, a pressure of 10 kg / cm ^2, a liquid hourly space velocity (LHSV) of 2.0 and a ratio of hydrogen to fuel of 7.0, during the reactivation was performed 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, was supplied. Then, a 2.0 volume percent oxygen-containing nitrogen stream and then for 3 hours at 510 ⁰ C was passed a stream of air through the catalyst for 2 hours at 430 ⁰ C. 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 carried out under the same conditions as in Example 1, with the exception that when the catalyst was reactivated, the treatment in the initial stage was carried out at 500 ^° C. for 5 hours and the treatment in the later stage at 580 ^° C. for 5 hours .

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 as in Example 3, with the exception that, when reactivating the catalyst, the treatment in the first reactivation ^{stage for 1 hours at 500 °} C. and the treatment in the later stage for 3 hours Hours at 580 ⁰ C was made. The following reaction results were achieved:

Catalyst Aromatic 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, Zi

, £ 509 624/1

9 10

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

burns, a catalyst of the composition catalyst aromatics yield

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

of 10 nil 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 Jj1 2 application suggested. For example, al: Patent claims: reactivation method for platinum-aluminum oxide catalysts or a third component contained 1. Process for reactivating a carbonate platinum-alaminium oxide catalyst, the hydrogen conversion used, is currently widely used in the reforming reactor, of 0.01 to 3 percent by weight of platinum, 0.01, usually an oxygen reaction up to 5 percent by weight lead and a third component method and a halogen reactant, -! Gsmethodj nente contains and a weight ratio of lead applied. In the first-mentioned method it is necessary to have platinum from 0.1 to 3, characterized by the use of an absorbent ent that carbon deposited in a first io-holding gas is carried out at a high level during,? to burn up to 5 hours at 300 to 450 "C temperature for a long time. Di <a OjSbisSVolumprp ^ ient oxygen-containing long-lasting treatment of a catalyst in gas and then in a second stage at high temperature promotes the sintering of the active 1 to 3 hours at 450 to 550 ⁰ C a 5 volume species and as a result accelerates the rate of the gas containing percent or more oxygen 15 long-term deactivation. 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. Such an amount is passed through the catalyst that it is assumed that the phenomenon is the cause of a 0.1 to 10 percent by weight halogen, based on long-term deactivation, which is disadvantageous. Andean catalyst. 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 as is based on the addition of chlorine and the like to the active 550 ⁰ C under a pressure of 1 to 20 kg / cm * species in order to bring about an acidic function, as carried out will. Hydrocracking, isomerizing, cyclizing and the like Although these two methods described above are widely used, they lose industriel 30 began to use common catalysts of theirs