DE1767729C3 - Process for the production of a catalytic converter for the afterburning of exhaust gases - Google Patents

Description

? f

_HO -L ₍₎ "-Lo"

where R is a hydrogen atom, a hydroxyl or alkyl group, R 'is a hydrogen atom, an alkyl or carboxyl group and η is an integer from 0 to 6, or its derivative, subsequent drying, calcining and reducing, dadur ch as geke η η ζ Eich η et that the alumina carrier either before or after impregnation with the aqueous solution of the platinum compound and the dicarboxylic acid or its derivative with an aqueous solution of a calcium, strontium or barium compound in an amount of 1 to 20 »/», related on the weight of the clay, soaks and then dries the catalyst

2. The method according to claim 1, characterized in that the alumina carrier with emer aqueous calcium, strontium or barium hydroxide solution drank.

3. Use of a catalyst prepared according to claim 1 and 2 for afterburning lead-containing engine exhaust gases. * °

Strontium ^^ ^ _g

from to 20 / ", \ ^ _dries

drank undl oan_ _ehen incorporating one

^ Z SuZ "or barium compound In the calcium ^ ^ron "" ^ra _da ß the catalyst S strength and a good J ^ SlSLl that they their kata.y-

? ^ J? SfSS preserve and that both night Activity long heritage ^ ^^ ^

combustion of exhaust gas lead absorption

Further fuel used _Kata ,

^^^? f _at ir as a layer within the TrS rinabettet and arranged on a defined distance carrier "njebette ^ unQ _{center point}

by £ Autejgeund vo ^^. ^ ^

J ^ ü ^ gSST distributed to the mass of

°, sLtpn ^, - ^ alkali compounds have the

Jen emahn en ErdalkaUvermn g ^ ^^

45

The invention relates to a method for producing a catalyst by impregnating a porous alumina carrier with an aqueous solution of a platinum compound in an amount of 0.01 to 10 percent by weight Platinum, based on the weight of the alumina, and simultaneous or previous impregnation of the alumina carrier with 0.1 'and 1.5 Gc ^ ickisprczsnt, related on the weight of alumina, a dicarboxylic acid of the general formula

ORO

Ii i Il

HO - C - (C) /, - C - OH j

wherein R is a hydrogen atom, a hydroxyl or alkyl group, R 'is a hydrogen atom, an alkyl or carboxyl group and η is an integer from 6 to 6, or a derivative thereof, followed by drying, calcining and reducing.

Catalysts ais Deswnucis _£ ul _& vw _& ..-. proven. In a further embodiment of the invention, it is also advantageous to impregnate the alumina carrier with an aqueous calcium, strontium or barium hydroxide solution.

The catalyst is preferred for the afterburning of lead-containing engine exhaust gases, i.e. of gaseous CO-hydrocarbon mixtures, used before they are released into the atmosphere. But the invention is also applicable if other gas mixtures containing hydrogen, ζ. Β. Exhaust gases from the petrochemical industry or from printing and tanneries that contain unsaturated hydrocarbons, Alcohols, ketones, aldehydes, acids as well as carbon monoxide and oxides of nitrogen and May contain sulfur, be subjected to a conversion before being released into the atmosphere have to.

In the catalytic treatment of exhaust gases, the catalyst mass is usually transferred to a Be-60 Container or catalytic converter introduced and installed in the exhaust line in such a way that the exhaust gases flow through. The catalytic converter can work with longitudinal flow, transverse flow or radial flow. at The converter can be used to convert exhaust gases from an internal combustion engine Additional component or connected to the usual silencer. Combustion air is in front of the converter inlet usually by a suction device

3 4

device or an external compressor, and writing 2 620 314 is described. In the interest of

the waste products go along with air due to simplicity and clarity limited to the following

the catalyst upstream or downstream, cross-explanatory on the use of alumina as

current or radial flow. When used with other refractory oxide carriers.

Purposes, e.g. B. to treat the waste gases from the 5 To impregnate the carrier with the barium, Stron printing, Tannery or petrochemical industry tium or calcium compound is used z. B. The catalyst mass can expediently as a fixed one of the hydroxide, formate or nitrate. The time to Layer inside the chimney or any other way of absorbing the aqueous solution should be 1 or 2 hours, Abfährleitung a combustion chamber arranged better be 4 to 20 hours. After soaking so that the products of combustion before their ab- io is the mass by heating, z. B. in a rotation to the atmosphere mixed with air through the evaporator, dried.

Paint catalyst. If desired, halogen can be added to the alumina, especially the incorporation of the active metal, before or after being influenced by a large number of factors. By the environment in which the catalyst is used i _S halogen addition is generally carried Verwird. For example, a vehicle combustion application of an acid such as hydrogen fluoride and / or an engine is usually over a wide range of hydrogen chloride and a volatile salt, such as speeds and load conditions, ammonium fluoride and / or ammonium chloride, and such as idling, brisk driving, acceleration and the Halogen can be operated with the clay while it is slowing down. Combustion effects 20 manufacturing are combined. In another manufacturer of such a machine, the order in which the halogen can vary considerably with a refractory. Space velocity and temperature of the oxide during its impregnation with the active metal Auspuffgasleitunjj as well as the concentration of combustibles are brought together. For example, the Materia! also vary in relatively wide- alumina from an alumina hydrosol with a geten limits. Therefore, if one prepares the catalyst for a weight ratio of alumina to chloride of about 1: 3 treatment of the exhaust gases of an automobile.

motors are used, the catalyst must have high tem- When impregnating the preformed alumina carrier

temperatures on the order of about 870 to with the water-soluble platinum compound and the

1070 ⁰ C, and it should be high dicarboxylic acid, it should be noted that the platinum compounds

Activity even at significantly lower temperatures with the carrier not before the addition of the di-

have doors. The catalyst is said to be a relatively carboxylic acid that the treatment is combined with

Have a low threshold temperature so that the dicarboxylic acid is needed before or during the addition

agile conversion reactions take place within the aqueous solution of the platinum compound, half the shortest time following the start of the For easier handling and dimensioning

Trigger the machine under relatively cold conditions. 35 the dicarboxylic acid in the required quantity with the

The catalyst must therefore truer your particular water-soluble platinum compound mixed and the

Period of time at one temperature to be effective, the impregnation solution obtained with the carrier material

considerably (between about 93 and 1100 ^c C) fluctuates. As water-soluble platinum compounds

can ken. if you use chloroplatinic acid, chlorine

In the preparation of the catalyst mass after the 4 ° platino acid, platinum chloride, fiatin dichloride. Invention is a refractory, inorganic as a carrier. Malonic, succinic,

cal oxide is used, the apparent bulk density of which is glutaric, adipic, pimeline, suberic, apple, tartar,

is less than 0.4 g / cm ³ and preferably between 2-methyl amber, 2,3-diethy! amber, 2,2-di-

0.15 and 0.35 g / cm ³ . It can serve by separate, methyl succinic acid. Oxalic

CIUV q Q g, t ^ V 3O.KXI \. UUV.1 TT Cl ti 3d Ul V WI) Jj

if there are two or more inorganic citric acids. Also mixtures of two or Includes oxides. The carrier material! can of course before - several of these acids can be used, Coming substances such as clays or earths contain non-alkaline soldering agents as thinners and, if necessary, prepare a solvent such as water, alcohol or a ^ clay before use. or several treatment methods, such as drying, 5 ° pulled.

Caicination, dampening or treatment with reactants that are activated in admixture with the various water-soluble reactants. The binding of the catalytic metal and the carrier catalyst mass according to the invention uses preferred material amount of dibasic acid to be used, such as an alumina, refractory carrier material such as tartaric acid, is based on the weight of the carrier where the term "alumina" is a very porous aluminum 55 related. It is in the range from about 0.1 to 1.5 weight percent geminium oxide in various hydration stages. The middle part of the area is summarized. Other refractory oxides such as silica, preferred, and a range from about 0.13 to boron oxide, thorium oxide, titanium oxide, zirconium oxide, 0.70 percent by weight of the support material, nium oxide and their mixtures can be used together with the amount of the catalytically active metal constituent Clay can be used. This other hot 60 partly platinum is based on the volume of the oxides to be solidified with it within the carrier material in some carrier material and is calculated as an elemental amount of about 0.5 to 25.0 percent by weight, tares metal, regardless of whether that is in particular of about 1.0 to 10.0 percent by weight, platinum as a complex with the carrier material or in the finished carrier. The carrier can be in the form of elemental state. As an example! be one of balls, tablets, extrusions, granules, amount of about 0.055 to 2.2 g per dm ^{3 of} carrier material, cakes, briquettes, rings, etc. have. That is to say, about 0.01 to 1.0 percent by weight of a spherical shape is preferred, which can be obtained in the range from about 0.15 to about 0.15 to 35 g using the known oil-free alumina method / cm ³ called density. The preferred concentrate

5 6

tration range of the platinum compound, as it is possible from the alkaline earth with the alumina! already at

economic considerations results, is to unite about the manufacture of the base. The ones in the

0.16 to 0.66 g per dm ^{3 of} carrier material. Embodiments described catalytic

According to an example, the catalyst was prepared by the following test method

by first rating alumina spheres of about 5, which mimics real-world driving conditions.

1.6 to 3.8 mm from an aluminum chloride hydrosol A standard dynamometer is used,

with a weight ratio of aluminum chloride whereby an eight-cylinder internal combustion engine

of about 1.25 shapes. ne is loaded by a motor generator. Uncomfortable

The alumina spheres are continuously produced about 440 cm ^3. Portions of each catalyst are adjusted by evaluating drops of the hydrosol in an on io zein, by allowing each catalyst to fall into an elevated temperature oil bath and cylindrical vessel or converter with one of the tropics begins within the oil up to coagulation to a clear width of about 100 mm; holding back the whole hydrogel balls. The balls are switched on when the device is dried in series in the engine exhaust pipe at a temperature of about 93 to 4? 5 ° C. In any case, the catalyst sample in and out at a temperature of about ur · 425-15 converter on a carrying wire to a layer height is calcined 650 ⁰ C. 150 g of clay .π are arranged over about 5 to 8 cm. A second sieve lies overnight, about 16 to 20:> «. U, iden, in one on the catalyst layer, around the catalyst of the impregnation solution of barium hy -λ-. e * -c soak up the ceramic balls by about 6 mm to separate them. Then they are dried at about 93 ° C until the even distribution of the 235 ° C is facilitated, in order to obtain 6% barium of the exhaust gas mass-weight flowing down through the device. A soaking solution from serve. Four converters with a catalyst containing chloroplatinic acid with a concentration of 0.0628 g are sent in a given test period. Platinum per cm ³ is used by diluting 3.0 cm ³ . This technique allows about 500 cm ^{3 of} water to be prepared at the same time. In use, ¹ TUfUHg various Kate.ysatoren and g for about 150 alumina Bariumku returns ₀ ELN of an as excellent basis for / ergleichsstudien the apparent bulk density of about 0.29 g / cm ³ provides results.

This concentration of the chloroplatinic acid solution in combustion air is poured into the converter inlet in a finished mass with about 0.35 g of platinum per dm ³ spheres - a flow rate adjusted in this way, chlorine-alumina carrier. The chloroplatinic acid presses that the mean temperature of the catal; Ator solution is maintained with about 0.52 g citric acid or about 30 layers at a level in the range of about 425 to 0.35 weight percent based on spherical weight, 920 "C. Preferably, the flowmixed. The resulting mixture of citric acid, speed the Verbreanungsluft constant at chloroplatinic acid and alumina Bariumkugeln is held kg in approximately 2.7, so that the average temperature of a rotary dryer at a temperature of 38 to the catalyst layer at a height of about 510 ^c C 121 ° C, preferably at about 100 ⁰ C is kept to dryness 35th the evaporated used in the test procedure. When the balls outwardly dry fuel is a blend of 40.0 ° / ₀ appear catalytically, commonly about 2 to 8 hours reformed gasoline, 40.0% catalytic cracked If this is the case, the impregnated balls are preferred gasoline and 20.0 ^{% alkylate with 3.0 cm 3 of} tetraethyl in a hydrogen atmosphere, reducing lead to 3.8 liters .

acts while keeping the temperature at a height of 40 Since the concentration and burnt coal in the Btreich increases from about 93 to 980 ⁰ C and these hydrogen and other harmful products keep in the temperature about 2 hours. In contrast ζ: exhaust gases as well as their throughput according to known production methods for catalytic the physical state of the machine, that is, the catalyst according to the invention is dependent on idling, acceleration, brisk travel no oxidation treatment at elevated temperature 45 or slowing down, the test or high temperature calcination is in subjected to an air process, the actual sifaßen conditions nor atmosphere. A Hochtemperat'iroxida- further approximated by the fact that a constant beta treatment tends to destroy the initial load only during part of the entire test period activity and especially the durability of the planned. Gas samples from the converter inlet and catalyst mass with regard to the distance or 5 ° outlet are taken at different time intervals during the conversion of harmful constituents into combustible rend the test method, while an exhaust gas. In addition, oxidation in air would require the constant analysis of the carbon monoxide concentration catalyst mass with nitrogen! takes place at increased temperature. The samples are brought into contact with hydrocarbons, and as already mentioned, substances are analyzed by a flame ionization detector, such treatment easily leads to destruction, whereby all hydrocarbons are detected, the kaiibarkcii the küüysatonsässc. It does not matter whether it is """saturated, unsaturated or partially

In the example shown, the carrier will be oxidized first. The carbon monoxide concentration in soaked with the earth-potassium compound. As already mentioned for the exhaust gases through an exact infrared, the impregnation can be determined with the alkaline earth detector ». The internal combustion engine connection but also after the treatment with the 60 is operated in a certain cycle in order to take place empty aqueous solution of the platinum compound and the dip! The simultaneous addition of the samung according to the experience with practical alkaline earth compounds, the platinum compound and the siren conditions must be demonstrated. During the dicarboxylic acid is prohibited, because otherwise the acid whole test procedure, which would be neutralized by the alkaline component for a period of time. 65 includes 40 hours, about 11361 of the named also catin the combination with the barium after the fuel are used. The 40-hour test period drying but before the hydrogen reduction treatment is divided into 8 cycles of 5 hours; every 5 hours or after reduction. Furthermore, it's dige cycle consists of 4 ^x / ₂ hours of brisk driving

constant 2500 rpm, and 41.5 PS -nd cincm '/ zSiün- amount of chloroplatinic acid of a concentration of digen cycle, consisting of a series of 15 cycles 0.0628 g platinum per cm ^{3 was} soaked, which is sufficient from 2 Minutes for idling at 750 rpm, acceleration to deliver a catalytic converter with 0.35 g platinum per dm ³ tonnage on a brisk journey at 200 rpm, and demand earth. For every 150 g of clay balls, the samung was set to idle at 750 rpm. 5 required amount of chlorinated acid to 5C0 cm * with

Because of the applied small catalyst space water diluted. Before the impregnation, the impregnation amount is the space velocity with the solution for the catalyst R 1 with 0.22 weight catalyst coming into contact exhaust gases bc- percent citric acid, based on the total amount considerably higher than under practical driving conditions the toner particles are mixed. The catalyst mass gen. Accordingly, that during a practical io was then used in a rotary dryer in a Tcmpe-application Evaporated to dryness in vehicle exhaust gas converters to a temperature of around 1Ü0 C / ur. Under The percentage conversion was considerably higher. The increase in temperature to 510 C became the limit The results obtained from the 40-hour test process were excluded from the hydrogen atmosphere; nits supply, semi-logarithmic in; incm coordinates- the hydrogen treatment was carried out for 2 hours at system plotted a curve from which the following »5 540 C continued. Finally left the catalyst equation derived: mass cool before exposure to air.

When testing the catalytic converters according to the

C - Ac '* applied methods it was found that the catalyst R 1

an initial hydrocarbon conversion of

In the equation, k is the reciprocal slope value, 10 73.8% and after 40 hours a conversion A is equal to the initial percentage conversion of 51.1%, while the shelf life, which is obtained by extrapolation, C is the same factor was equal to 108.7. The carbon monoxide conversion percentage conversion in the Zcit (r) and lung was initially 88.2% and after 40 hours f means the time in hours. «9.9% with a durability factor of 172.7. To

The above equation is used to calculate 25 40 hours, the room reverberation was 10.7%. The stability factors of A for the individual catalytic peripheral crush strength became 1.0 kg gctic masses. A decrease in the slope of the fun ^ n.
Curve obtained from the values obtained,

or vice versa, a cm increase in the Α value means that Example 2

a catalyst has a greater degree of stability, 3 °

when he burns the carbonaceous combustion- In this example, the alumina balls were added.

products of an internal combustion engine are treated with barium hydroxide overnight, delt. If the A stability factor is positive, which is a positive and then washed and dried, so that one indicates a tive tendency, this means that the stabilized alumina-barium oxide base with about 4.6% of the evaluated catalyst increases over time Received barium. This document was increasing. Although a great difference between the catalyst masses then impregnated with chloroplalinic acid and citric acid has a relatively high initial activity, the latter having a molar ratio, the durability of such catalysts is such that from about 3: 1 acid to platinum and 0.35 g that the tolerable maximum limits which the carbon platinum ^{supplied per dm 3 of} alumina. The resulting katalylenehydrogen and carbon monoxide concentrations of 4 ° active mass were then dried and set in a relatively short period of time - the presence of hydrogen reached approximately 2 hours at a span. about 540 C reduced.

The alumina spheres about 3 mm in diameter, when tested, the catalyst showed an initial

The hydrocarbon conversion of 64.3% and used as carriers for the He masses of the following examples were produced by the same method after 40 hours of conversion of 60.4 ° / ₀ , which provided and had practically the same physical stability factor k is 644.2. The charcoal properties and low apparent bulk density oxide conversion was initially 71.4% and then on the order of 0.28 g / cm ³ . 40 hours 65.8% with a stable factor of

To the physical strength of the various 485.8. Even after a period of 40 hours, the catalyst masses had to be evaluated, the lead retention was represented by 7.0%. It can therefore be determined that the test samples are subjected to a standardized test procedure, with the result that, in comparison with the reference catalytic converter dip, they are held in place in order to clearly improve the "peripheral crush resistance" (PCS) and to determine the lead retention. The mean crush strength of one is lower. The peripheral crush strength of the particle is found to be 1.4 kg as the arithmetic mean of the force, which is also clearly better than that determined for crushing each particle of a 55 of the reference catalyst.
given number of individual particles is required.

Each particle is crushed in an apparatus, F. e i s ρ i e I 3

which is built in such a way that the force

nuieri; ch and at a steady speed.

starting with a zero load. 6 ° next with a calcium hydroxide solution overnight

treated and then washed and dried to

Example 1 ^a pad with 5.0 percent by weight calcium

Yeasts. This pad was then coated with chloroplatinum

In order to treat reference catalysts for comparison to acid and citric acid in such amounts, use improved catalysts with an additive that a molar ratio of 3: 1 of the acid to the constituent of calcium, strontium or barium to platinum was obtained and the resulting mass Providing 0.35 g of platinum, a catalyst R 1 was prepared by containing ^{3 alumina per dm.} The mass was then dried with alumina balls about 3 mm in diameter and with hydrogen for about

ίο

Acid solution soaked at a molar ratio of citric acid to platinum of 1.25, so that one a reduced mass with 0.52 g of platinum per dm "of clay received. The mass was then treated with beryllium oxide, the beryllium. . Formate through Dissolution of beryllium hydroxide in formic acid was used. Contained after rinsing and drying the mass about 5% beryllium oxide.

,. In the test method it was found that the

retention after 40 hours was 7.49%. The initial conversion of hydrocarbons with io 74.2% Calcium-impregnated catalyst of this game shows and after 40 hours 40.7% with a stability

· - '■ - · «<·« * fc-rfiK. factor of 66.6. The carbon monoxide wall

The initial rate was 81.1% and after 40 hours

Hours at a temperature of about 540 ⁰ C reduced.

In the testing procedure, the catalyst showed an initial hydrocarbon conversion of 64.1% and after 40 hours a conversion of 60.3% with a corresponding shelf life factor of 663.1. The carbon dioxide conversion was initially 77.1% and after 40 hours 71.7% clrt2m shelf life factor of 557.8. The lead back

Calcium soaked catalyst this p g

ilso a high durability and a significantly reduced one Lead retention in comparison with the pull-out catalytic converter. The peripheral crush strength fc was 1.7 kg.

g ar initially 81.1 / _{0 a}

77.4 ° / ₀ with a stability factor equal to 215.6. The lead retention after 40 hours was i Z

Example 4
The alumina balls of this example were initially 10.9 ⁰ Z ₀ . The crush strength was 2.1 kg. Again, the mass of this example shows relatively low stability factors, especially for the carbon

The alumina balls of this example wuiucii iuiiav-1131 hydrogen conversion. while the lead is treated with a strontium hydroxide solution overnight in comparison to the calcium, strontium or catalyst masses containing a strontium content of 4.5% barium. after washing and drying performed. Then the alumina-strontium oxide mass was in the
in the same way as in the previous examples
Chloroplatinic acid and citric acid treated so that 25
a dried and reduced mass with approximately
0.35 g of platinum was ^{poured per dm 3 of} clay.

The quay analyzer test showed an initial carbon

hydrogen conversion of 70.4% and after 40 hours. ,,, .-. ,

the. a conversion of 59.7% with a Stabili- 30 with 0.52 g of platinum per dm ^{3 of} alumina after drying and an efficiency factor equal to 244.1. The carbon monoxide conversion into hydrogen was obtained. The mass was initially 79.8% and after 40 hours
91.7% with a stability factor of 383.2. The lead retention was after 40 hours of testing
5.87%.

Example 7

In this example the alumina balls have become fragile with chloroplatinic acid and citric acid in the same molar ratio as in the previous example treated so that you get a platinum-alumina mass

Obtained reduction in hydrogen. The mass was then treated with barium oxide as a formate solution. which was formed by dissolving barium oxide in formic acid. The rinsed and dried mass can be removed 5% Biid

Aging was formed after 40 hours of testing. It should be noted that the strontium-containing 35 contained approximately 5% barium oxide

biliä lih during the examination showed

The test showed that this catalyst composition initially provided a hydrocarbon conversion of 75.8% and after 40 hours of 69.1% with a stability of 429.2. The conversion of Konlenmonoxid-40 was initially 75.9% and after 40 hours 80.7 ⁰ Z ₀ with a stability factor of 650.7. The lead retention was 7.95% after 40 hours. The crush strength was 0.9 kg. It is to be bemer-111 uiuui. U ^ r- - ken that the present catalyst is proportionate

next with lithium hydroxide for a long enough time. Favorable compared to the other calcium, electricity

handeil. around an alumina-lithium oxide mass to ergetium and barium masses. where such oxides under

ben. after washing and drying approximately

Contained 5% lithium. The received pad was

then as above with chloroplatinic acid and

Citric acid treated to 0.35 g of platinum per dm ³

To give clay after drying and reduction.

Mass also has good activity and stability at the same time with a low lead retention compared to supplies the reference catalytic converter. The crush strength was 1.7 kg.

Example 5 In this example, the toner spheres were

UUIIl- UUU DilllllllllliasStll IM. VVU JUIlIIt UAiu

Using the hydroxides were formed.

Example! 8th

Hydrogen conversion; £ 65 / "

find hours ^ 40 According to this example, the clay balls were initially mixed with chloroplatinic acid and citric acid the white of the two previous examples.

Living _example

Munw ^ nm ^ Jf ^ wonh ^ graced with a stability factor

UlCr \ .UlllClllllUllu / iluu ..... _u .. _{c w}

lind after 40 hours 64.2% with a stability factor from 202.4. Lead retention was after 40 hours Test duration 9.3%. Similar to magnesia, lithium oxide does not seem strong in the catalyst mass Buildable catalyst, especially for hydrocarbons Conversions deliver, and lead retention is relatively high compared to that Masses of Examples 2. 3 and 4.

Example 6

According to this example, the alumina balls were first treated with a chloroplatinic acid and lemon

graced. _a "

treated sium oxide as formate for a sufficiently long time, to provide a mass with approximately 5% magnesium after washing and drying.

When tested, the catalyst initially showed a hydrocarbon conversion of 76.8% and after 40 hours of 56.3% with a stability of 129.1-The carbon monoxide conversion was initially 80.6 ⁰ Z ₀ and after 40 hours 76.7% with a stability factor of 811.1. The lead retention was 9.46% after 40 hours. The crush strength was 0.8 kg. Again it should be noted that the catalyst composition, of this example, is a relatively poor carbon

11 12

Hydrogen conversion stability and relative Example 11
showed high lead retention.

In this example, the clay balls were made with

Example 9 of a chloroplatinic acid and citric acid in one

5 molar ratio of 3: 1 treated so that one

In this example, two different cata- a mass with 0.35 g of platinum per dm ^{3 of} alumina was calcined after analyzers at high temperature and the drying and reduction according to the above results were compared. In one case an example was received. This platinum-alumina mass was then prepared in the standard form of a platinum-alumina catalyst with a calcium hydroxide solution of 2 percent by weight calcium oxide based on the weight of the clay, corresponding to the catalyst R1 of Example 1. Subsequent to the reduction stage, the earth content of the mass was treated overnight during a catalyst, but at a high temperature for a period of 16 to 20 hours, and calcined at about 98O.degree. A second batch of catalyst was then rinsed, dried and at a temperature was prepared in the manner indicated, but calcined on the order of about 540.degree. the platinum-alumina mass with barium hydroxide 15 The analysis showed 1% calcium of the mass,
In the beginning, the test method showed a hydrocarbon conversion of 68.3% after drying and reduction and after 40 hours of mass with about 5% barium oxide. This conversion of 61.5% at a stability level is also at a high temperature of about a factor of 385.9. The carbon dioxide conversion 980 ^J C calcines. 20 was initially 74.9% and after 40 hours 77.7%

The test method showed that the catalyst had a stability factor of 1077.4. The lead back initial carbon retention without the addition of barium oxide was 8.76% after 40 hours. The crushed hydrogen conversion of 59.9% and after 40 hours of strength was 1.1 kg.
which yielded a conversion of 32.8% with a stability factor of 66.4%. The carbon oxide 25 B is ρ 1 e I 12
conversion was initially 72.6% and gradually increased

40 hours ^ 0.7% with a stability factor of The alumina balls were with a platinic acid

112.6. The lead retention after 40 hours and citric acid was in the molar ratio of 3: 1

10.8%. treated so that you get a mass with 0.35 g of platinum

On the other hand, the catalyst mass with the 30 dm ^{3 of} clay after drying and reducing

Barium oxide initially obtained a hydrocarbon wall according to the previous example. This

of 65.7% and after 40 hours of 61.6% in the case of platinum-alumina mass, a calcium

a stability factor of 611.6. The carbon hydroxide solution containing 10% calcium oxide des

The initial monoxide conversion was 72.9% and the weight of the alumina content of the mass was overnight

after 40 hours 69.3% treated with a stability factor of 35 for 16 to 20 hours and then

of 777.0. The lead retention was rinsed after 40 hours, dried and at a temperature in the

the 7.20%. The crush strength was 1.5 kg. Calcined on the order of 540 ^° C. The analysis

The catalyst containing barium oxide thus showed the mass showed 3.0% calcium,

considerably greater stability and less lead. The test method showed initial carbon retention even after calcination with a hydrogen conversion of 70.9% and after 40 hours

high temperature compared to the standard, which has a conversion of 63.4% with a stable

catalyst without the addition of alkaline earths. efficiency factor of 358.6. The cooling monoxide conversion

was initially 73.1% and after 40 hours 74.6%

Example 10 a stability factor of 1926.9. The lead back

45 retention was 8.92% after 40 hours and the

In this example the alumina balls with crush strength was 1.7 kg.
Chloroplatinic acid and citric acid in one molar
Ratio of 3: 1 treated in such amount that

0.35 g of platinum per dm ^{3 of} clay in the dried example 13
"Mass obtained. The clay so soaked in this way became an- 50

then at a temperature of about 93 to The alumina balls were ^{dried with a chloroplatinum 150 0} C and treated in the presence of hydrogen acid and citric acid in a molar ratio of about 2 hours at a temperature in the 3: 1, so that a mass reduced with 0.35g order of about 540 ⁰ C. The platinum per dm ^{3 of} alumina after drying and Rcduk platinum alumina catalyst was then obtained with a 10% ion according to Example 10. This barium hydroxide solution containing platinum-barium oxide and alumina mass was then treated with a calcium hydroxide and allowed to stand for 10 to 20 hours overnight with a solution containing 30% calcium oxide by weight. The platinum-alumina Bariumoxidmasse of the alumina content of the ground during overnight was then rinsed, dried and treated to produce 16 to 20 hours and rinsed out and calcined catalyst at about 980 ⁰ C. 60 dried and at a temperature in the size

The test method initially showed an order of hydrocarbons of 540 ° C calcined. Analysis of the mass

Conversion of 65.0% and after 40 hours showed 8.5% calcium.

a conversion of 59.5% with a stability The test method showed an initial carbon factor of 451.0. The carbon monoxide conversion to hydrogen conversion of 42.9% and after 40 hours initially 68.9% and after 40 hours 67.1% in 55 den of 13.8% with a stability factor of 35.4. a stability factor of 1550.7. The carbon monoxide conversion was initially retention was 6.74% after 40 hours. The reduction 46.9% and after 40 hours 21.5% with a stable squeeze was 2.3 kg. efficiency factor of 51.2. The lead retention was fraudulent

13 V 14

after 40 hours 5.66% and the crush strength indicated a conversion of 35.5% with a Stabiliw & r 1.8 kg. capacity factor of 317.6. The carbon monoxide conversion

was 45.1% initially and 45.8% after 40 hours

Example 14 has a stability factor of 3888.9. The lead back

5 retention was 6.41% after 40 hours, and the

The clay balls were made with a chloroplatinum crush strength of 1.6 kg. acid and citric acid in a molar ratio
treated by 3: 1, so that a mass of 0.35 g of I

Platinum per dm ^{3 of} clay after drying and reduction B eis ρ ie 1 17 |

jff obtained according to Example 10; This platinum-alumina mass ίο 1

Ij was then treated with a strontium hydroxide solution, The alumina balls were washed with chloroplalic acid 1

holding 2% strontium oxide of the weight of the tonic and citric acid in a molar ratio of 3: 1 treated, I crdegehaltes of the mass overnight for 16 to so that one ^{treated a mass with 0.35 g of platinum per dm 3} ton-] 20 hours and then rinsed , it dries after drying and reducing according to example j and obtained at a temperature in the size range 10. This platinum clay was! Calcined order of 540 ° C. The analysis of the fair then with a barium hydroxide solution that 2% Ba- ■ showed 1.1% strontium. rium oxide of the weight of the tonenie content of the

The test method showed an initial mass of carbon as in the previous examples Hydrogen conversion of 67.0% and treated further after 40 hours. Analysis of the calcined mass j that of 63.0% with a stability factor of 649.2. 20 showed 2.3% barium. '

The carbon monoxide conversion was initially The test method showed an initial carbon

73.2% and after 40 hours 78.0% with a hydrogen conversion of 68.5% and after 40 hours Stability factor of 623.3. Lead retention was 63.7% with a stability factor of 549.8. j

was 8.76% after 40 hours and the crushing The carbon monoxide conversion was initially j

strength was 1.1kg. 25 74.5% and after 40 hours 78.4% for a y

Stability factor of 792.0. The lead retention after 40 hours was 9.19% and the crush rate Game 15 strength was 1.0kg.

The alumina balls were made with a chloroplatinum Example 18

acid and citric acid in a molar ratio of

3: 1 treated so that a mass of 0.35 g. The alumina balls were made in the same way as

Platinum per dm ^{3 of} clay after drying and reduction in Example 10 treated with platinum and citric acid, tion according to Example 10 was obtained. This platinum-alumina 35 and the platinum-alumina mass was then with barium mass was then with a strontium hydroxide solution containing 10% barium oxide of the solution containing 10% strontium oxide of the weight of the clay weight of the mass, as in the above for the alumina content of the mass Treated night during examples. Analysis of the calcined 16 to 20 hours treated and then rinsed, mass showed * 3.4% barium.

dried and at a temperature on the order of 40. The test method showed an initial coal order calcined at 540 ° C. Analysis showed hydrogen conversion of 65.6% and after 40 hours -3.1 % Strontium. that of 66.2% with a stability factor of 4400.0.

The test method showed an initial carbon monoxide conversion was initially 67.7% y

Hydrogen conversion of 68.5% and after 40 hours 76.1% with a stability j

40 hours of 64.6% with a stability factor of 45 factor of 343.9. The lead retention was according to ί

688.0. The carbon monoxide conversion was 8.92% at 40 hours and the crush strength was 69.6% initially and 74.9% after 40 hours for a 1.9 kg.
Stability factor of 549.9. The lead reluctance

was 8.40% after 40 hours. and the crushing. .

strength was 1.9kg. 5 * Example 19

The clay balls were prepared in the same manner as s

B is ε ρ 1 1 e j 16 _m foregoing example treated, j with the difference

decided that instead of 10% barium oxide, 30% barium oxide

The clay balls were used with a chlorine platinum 55. Analysis of the calcined mass

acid and citric acid in a molar ratio of 3: 1 showed 11.0% barium. j

and a mass containing 0.35 g of platinum was obtained. The test method showed an initial j

per dm ^{3 of} clay after drying and reducing hydrocarbon conversion of 64.0% and after!

according to Example 11. This platinum-alumina mass was 40 hours at 64.3% with a stability factor of j

then with a strontium hydroxide ^solution containing 30% 6o 8405.9. The carbon monoxide conversion was an- {

Strontium oxide of the weight of the alumina content of the catch 69.3% and after 40 hours 76.2% at a j

Mass contained, overnight stability factor of 421.0 for 16 to 20 hours. The lead retention | treated and then rinsed, dried and amounted to 6.30% after 40 hours and the crushing

at a temperature of the order of 540 ° C the tightness was 1.7kg. ^;

calcined. Analysis of the mass showed 14.0% ⁶ S For a more convenient comparison of the values obtained 1

Strontium. for the various tests the results are j

The test method showed an initial charcoal of Examples 1 to 19 in the following table (

hydrogen conversion of 40.3% ^and after 40 hours together;

16

Example no. , Type of catalyst

10

11th

12th

14th

15th

KoWen hydrogen conversion A; 4OStd. J K

CO conversion A I 40h I K.

% Lead retention

Crush strength chain

kg

»R 1« ALO ₃ + 0.35 g Pt / dm ¹ + citric acid

3 _a i- Ba (OH)., + 0.35 g Pt / dm ³ "τ citric acid (4.6% Ba)

AI ₂ O ₃ + Ca (OH), + 0.35 g Pt / dm ³ + citric acid (5.0% Ca)

AI ₂ O ₃ + Sr (OH) ₂ + 0.55 g Pt / dm ³ + citric acid (4.5% Sr)

Al ₂ O ₃ r Li OH + 0.35 g Pt 'dm ³ + citric acid (5% Li)

ALO ₃ + BeO + 0.52 g Pt / dm ³ + 1.25 citric acid (5% BeO)

AI ₂ O ₃ + 0.52 g ft / dm ³ + citric acid + BaO as formate (5% BaO)

Al ₂ O ₃ + 0.52 g Pt / dm ³ + citric acid + MgO (5% Mg)

P 1 «Al ₂ O ₃ + 0.35 g Pt / dm ³ + citric acid

calcine at 980 ^° C. Al ₂ O ₃ + 0.35 g Pt / dm ³ + citric acid

73.8

64.3

64.1

70.4

65.9

74.2

75.8

76.8

59.9

calcine at 980 ⁰ C (5% Ba)

Al ₂ O ₃ + 0.35 g Pt / dm ³ + citric acid + Ba (OH) ₂

calcine at veu ° <

(10% BaO)

Al ₂ O ₃ + 0.35 g Pt / dm ² + citric acid

/ - _ ir \ U \ ΙΛ nOI Ca \

Al ₂ O ₃ + 0.35 g Pt / dm ³ f citric acid + Ca (OH) ₂ (3.0% Ca)

AI ₁ O ₃ - 0.35 g Pt / dm ³

+ Citric acid

4 Ca (OH) ₂ (8.5% Ca)

Al ₂ O ₃ ■ 0.35 g Pt / dm ³

. Citric acid

J. Sr (OH) ₂ (1.1% Sr)

.Ai ₂ O ,. 0.35 g Pt / dm ³

Citric acid

i Sr (OH) ₂ (3.1% Sr)

65.7

65.0

Ag

70.9

42.9

51.1 60.4 60.3 59.7 49.7 40.7

69.1 56.3

32.8 61.6

59.5

108.7

644.2

663.1

244.1

141.4

66.6

429.2

129.1

66.4

611.6

451.0

88.2

71.4

77.1

69.9

65.8

71.7

79.8 71.9

78.3

81.1

75.9

80.6

72.6

72.9

68.9

64.2

67.4

80.7

76.7

50.7

172.7

485.8

557.8

383.2

202.4

215.6

650.7

811.1

112.6

69.3 777.0

67.1

63.4

13.8

63.0

64.6

358.6

74 Q 77.7

73.1

46.9

73.2

69.6

74.6

21.5

78.0

74.9

1550.7

1077.4

1926.9

51.2

623.3

549.9

10.7 7.0 7.49 5.87 9.3

10.9

7.95 9.46

10.8 7.20

6.74 8.76 8.92 5.66 8.76 8.40

1.0

1.4

1.7

2.1

0.9 0.8

1.5

2.3 1.1 1.7 1.8 1.1

1.9 409649/354

/ I /

IS

Example no. Catalyst type K
A. ohlenwasse
convert
[40h raw material
mg
I ^K C.
A. "-Conversion
J 40h IK 3888.9 % ßlei-
back-
holding Crush
strength
kg 16 AI ₂ O ₃ + 0.35 g Pi / dm ³
+ Citric acid
+ Sr (OH) ₂ (14% Sr) 40.3 35.5 317.6 45.1 45.8 792.0 6.41 1.6 17th Ai ₂ O ₃ + 0.35 g Pt / dm ³
+ Citric acid
+ Ba (OH) ₂ (2.3% Ba) 68.5 63.7 549.8 74.5 78.4 343.9 9 _; 19th 1.0 18th AI ₂ O ₃ + 0.35 g Pt / dm ³
+ Citric acid
+ Ba (OH) ₂ (6.4% Ba) 65.6 66.2 4400.0 67.7 76.1 421.0 8.92 1.9 19th Al ₂ O ₃ + 0.35 g Pt / dm ³
+ Citric acid
+ Ba (OH) ₂ (Il ₁ OVoBa) 64.0 64.3 8405.9 69.3 76.2 6.30 1.7

Claims (1)

1. A method for producing a catalyst by impregnating a porous alumina carrier with an aqueous solution of a platinum compound in an amount of 0.01 to 10 percent by weight Platinum, based on the weight of alumina, and simultaneous or previous soaking of the Alumina carrier with 0.1 to 1.5 percent by weight, based on the weight of clay, a Djcarbon acid of the general formula emgebeuei w ru, _{dje anyway} | _{from the a} ute _n catching Schicritjo ^ J ^ ^ _{des Katalvsator} _ flat als_au ^ _{Absland au} f _we is. The so share ens eu ^1C . However, _factors have only a ^a J _{1 n 's} durability and longevity. The invention consists in _{increasing the} lifespan of the known ^^^ _n », reducing the speed of the lysa _and reducing the lead in the afterburning of lead-containing ok