DE2130843A1 - Method of making a catalyst - Google Patents

Description

Patent Assessor 'Hamburg, June 21, 19? 1 Dr. G. Schupfner T? 1 027

2000 Hamburg? 6 (D 71.410-PB)

Sechslingspforte 2 JH / Pr 2 1308 A3

TEXACO DEVELOPiIENT CORPORATION

135 East 42nd Street New York, N.T. 10017

UNITED STATES.

Process for the preparation of a catalyst

The present invention relates to the production of fluorine-containing catalysts and their use in Hydrocarbon conversion processes at low temperatures. In particular, the invention relates to a method for the preparation of a catalyst suitable for hydrocarbon conversion which is an element of group VI B or VIII of the PSE, as well as aluminum oxide and fluorine.

Fluorinated catalysts are of interest in several Processes such as isomerization, reforming, alkylation, hydrogenation, disproportionation, cracking, polymerization and hydrocracking. So far, the fluorination of catalyst base material or mixtures with aqueous fluorinated water has been used FoijiT or evaporated boron or ammonium fluorides

109853/1895 - ₂ -

BATHROOM ORIGINAL ¹

performed. However, such fluorination techniques worked various problems such as health damage, handling difficulties due to the fluorinating materials used and the risk of corrosion on systems with himself. In some cases, undesirable deposits resulting from fluorination resulted in a malfunction the catalytic effect. Furthermore, these techniques were not suitable for use during high temperature regeneration lost fluorine. Recently, other fluorinating substances such as CF. and SF ^, suggested been. However, apart from the cost factor, these materials pose physiological problems.

The invention now consists in a catalytic activation of mixed material, wherein a fluorinating agent is used as part of the activation system, which the plant corrosion problems reduced. The invention also enables a catalyst fluorination process with an agent which is physiologically inert. The invention makes use of the fluorinating agent, which was previously considered inert to react with alumina. It is also a hydrocarbon conversion process in the presence of a catalyst prepared in situ or regenerated under non-corrosive conditions in a hydrocarbon converting reactor.

The invention relates to a process for the production of a catalyst consisting of a hydrogenation component, an aluminum oxide and about 0.5-15.0% by weight of fluorine, in which an aluminum oxide is mixed with a hydrogenation component consisting of the groups in groups VI B and VIII of the PSE existing metals, compounds of these metals or mixtures _{thereof, m} ± t a Mi-

_ 3 _ BAD OBIGtNAU 109853/1895

bag of hydrogen or oxygen and an organic fluorine compound having 2 - C-Atommbei a temperature of about 93 16 - 64-9 ⁰ C is reacted.

According to the process of the invention, catalytically active fluorinated catalysts can be prepared by an organic fluorine compound having the general formula

^C n ^F a ^H b ^X c or oxygen X: nitrogen η: 2 - a: 1 - - 1 b: 0 - c: 0 - - 16 - 2 η + m - 2 η + m - 1

is reacted with the catalyst base material. The value m is 2 when c = O or when X is oxygen, and is

3 when X is nitrogen. Compounds that are present as part of the activator system are difluoroethane, hexafluoroethane, Hexafluoroacetone, octafluoropropane, 1-fluoro-2-methylpropane, Decafluorodiethyl ether, hexafluorobenzene, hexadecafluoropropyltetrahydropyran, Heptacosafluorotributylamine and tritriacontafluorohexadecylaiain. It was found, that the organic fluorine compound is transferred in chemically reactive form in the presence of an element of the group VI B or VIII and hydrogen or oxygen, so that an alumina mixture is activated and chemically bound fluorine content of about 0.5-15.0, preferably 0.5-6.0% by weight based on the catalyst can be.

The highly active hydrocarbon conversion catalyst considered here s are obtained from an alumina mixture, which by a combination of hydrogen or oxygen and a fluorine compound has been activated. As indicated above, aluminum oxide is a mixture

- 109853/1895 - ⁴ ~

BATH ORIGINAL

component added from the group of metals of the ' Group VI B and VIII of the PSE, e.g. chromium, molybdenum, Tungsten, cobalt, nickel, platinum, palladium, ruthenium and rhodium are derived from. Combinations of these metals are also used considered as nickel - tungsten and cobalt-molybdenum. The elements present in the catalytic converter can. as a metal or as a compound such as oxide, sulfide or salt. such as sulfate. Preferably platinum and. Palladium used. In general, the elements of the Group VI B and VIII of the PSE containing catalyst these in proportions of 0.01 - 30% by weight, based on the metal, exhibit. If elements of group VIII of the PSE, such as platinum, palladium, rhodium and ruthenium, are used as components of the mixture, they are preferred. . 0.1 2.0 % By weight present. The combinations of metals like. Nickel and tungsten are used in larger proportions of e.g. B. 20-30% by weight applied.

.Aluminum oxides can according to the invention in various Molds can be used and especially those aluminas are useful which have displaceable surface hydroxyl groups and have surfaces of 50 - 800 m / gram according to the BET method. According to this definition, for example eta-aluminum oxide, gamma-aluminum oxide, SiOp-stabilized Alumina such as B. aluminum oxides with approximate ^ wt .-% SiOo, thorium oxide, zirconium oxide, titanium oxide and chromium oxide-aluminum oxide. SiOp aluminum oxides are also used with 100 - 600 m / gram surface and AIu-

Minosilicates with a surface area of 600 - 800 m / gram are included. Preferably aluminum oxides with a surface will condense from 50 - A-OO m / gram, especially eta- and gamma-aluminum oxide, used. Appropriate mixtures to be considered and to react with the fluorination system, include commercially available materials such as platinum, aluminum

- 5 -109853/1895

BATH ORIGINAL

oxide, reforming catalysts. The preparation of these mixtures is known. Example meadow, a metal such as platinum, is introduced into the mixture by impregnation of active AIuminiuinoxids applied -wherein an aqueous solution of chloroplatinic acid and Ithylendiamin, dried and is heated for two hours about '566 ⁰ C for roasting. This creates a platinum-coated aluminum oxide mixture. If palladium is used, the soaking is done in a similar way, using a palladium tetramine complex obtained by dissolving palladium chloride in HGl, diluting with water and concentrated ammonium hydroxide, heating to 45.6 C, stirring for 30 minutes until the precipitate that has formed is redissolved will. The resulting solution is cooled, added to the aluminum oxide and mixed with it, dried at about 140.degree. C. and then calcined for at least two hours at an elevated temperature of 427-649.degree. Similarly, the addition of elements of the group VI B of the periodic table, whereby impregnated with soluble salts of these metals and subsequently several hours at 216 to 649 ⁰ G is calcined.

The fluorination according to the invention increases the acidity of the treated mixture, thereby increasing the catalyst activity promoted and an improved selectivity is achieved. The fluorination gives a catalyst activity at low Temperatures at which non-fluorinated mixtures would be inactive. The fluorination continues in the presence made of hydrogen or oxygen, which are a component of the activation system; this allows activation in the absence of harmful carbonaceous deposits on the catalyst surface.

The ratio of hydrogen to fluorinating compound in the contact step can be from 0.5-100 gram-moles / gram-atom

109853/1895

BmD ORIGINAL

Fluorine in the compound, preferably in the range 2-10 gram-moles H _p / Gr anna-atom fluorine, vary. Hydrogen ratios of less than 0.5: 1 are undesirable, since no effective use of the fluorinating compound is possible. Likewise, ratios of 100: 1 are not necessary, ■ because the required optimum for hydrogen consumption is greatly exceeded. Similarly, the ratio of oxygen to fluorinating compound in the contact step / is set to be at least 1-50 gram-moles of oxygen / gram-atom of carbon in the fluorinating compound, preferably 2-10 gram-moles of oxygen / gram-atom of carbon. Oxygen ratios of less than 1 gram-mole are insufficient in the reaction between the alumina and the activation system, result in a slower rate and lead to incomplete activation. The stoichiometry of the activation reaction can be assumed in the sense that the fluorinating activating agent reacts with the hydroxyl groups present on the surface of the catalyst with the introduction of fluorine and the elimination of water and CO 2 or CO 2. Oxygen ratios over 50 are not necessary, as they far exceed the required optimum for oxygen consumption. The activation combination of hydrogen or oxygen and fluorinating compound can be introduced into the mixture either separately or as a mixed stream, the activation component flowing over and through the mixture. When hydrogen is used in the contact step, the temperature of the mix is generally 93 to 649 ° C, preferably 3I6 - 482 ⁰ C ,. set. When using Säuerst off / transmits the mixing temperature 232 - 4-82 ⁰ C, preferably 260-371 ⁰ C. The contact time depends on the applied activation temperature and the weight percent of fluorine to be introduced into the mixture, and is 0.5 .- 24 hour, preferably 2-7 hours. The catalyst

- 7 - 109853/1895 BAD ORIGINAL

tor is prepared in situ in a hydrocarbon conversion reactor, in which a stream of hydrogen or oxygen and non-corrosive fluorination compounds is blown directly into the boiler containing the mixture - The boiler effluent consists in the activation phase of water and methane or a carbon oxide such as CO or CO ₂ -

One means of activating the mixture is by contact reaction with a combination of hydrogen and fluorinating compound. Are not elements, the VI. or VIII. Group of the PSE is present in the mixture, the fluorination compound remains chemically inactive, especially at temperatures of 4-8 ° C. and lower, and the aluminum oxide only adsorbs the fluorination compound without a chemical bond occurring. If the fluorine compound is merely adsorbed on the mixture, the catalyst activity is neither brought about nor promoted, nor is the selectivity improved. Unexpectedly, when metal-aluminum oxide mixtures are treated with hydrogen or oxygen and the fluorination compound, the reaction between the fluorine compound and the mixture is brought about in an unknown manner, whereby the catalytically active material in question is obtained. The contact reaction will. generally carried out at temperatures of at least 93-64-9 ° C. When the contact reaction begins, hydrogen and fluorinating agents are preferably used at temperatures of at least 232 ^° C., as a result of which rapid fluorination of the mixture occurs. After a fluorine content of about 0.5% by weight has been reached, the temperature can be kept at 93 ° C. in the further contact reaction. However, the reaction proceeds more slowly at these low temperatures and leads to insufficient utilization of the fluorinating compound. If the initial or subsequent contact temperatures are below 93 ° C, the im

10985 3/1895

μ: ■■ '■ -Λ ·:.: . ", r- ~ BATH ORIGINAL

generally inadequate adequate reaction rates or none. obtained highly active catalysts for an economical process; the fluorine content is less than 0.5% by weight. In a particularly preferred embodiment, the contact reaction "is performed at temperatures of about 232 - 482 ⁰ C performed.

The invention can both initial activation and also concern the subsequent regeneration of the fluorinated catalyst. It must be remembered that in the draining hydrocarbon conversion starting materials are used, which in some cases contain foreign matter such as B. bound nitrogen in over 30 ppm proportions or Arsenic, antimony and other well-known poisons such as alkali or alkaline earth metals may be included in the process give cause for deactivation of the catalyst can. In order to restore the catalyst activity, the deactivating substances must be removed from the catalyst They are volatile fluorides by reaction with the combination of hydrogen or oxygen and fluorinating compound form.

The catalyst prepared according to the invention can be in tablet, granule or powder form for ease of use used in fixed bed, fluidized bed or in the fluidized bed. During the ongoing catalyst activation or regeneration, the gas leaving the reactor consists largely of methane, water, and CO and not converted fluorinating agent. Unreacted fluorine compound and excess hydrogen or oxygen can be circulated.

The catalyst produced by the process of the invention is highly active in hydrocarbon conversion

109853/1895

BATH ORIGINAL

at relatively low temperatures of 93-538 G and is used in a variety of conversion processes such as hydrocracking, selective hydrocracking, hydroisomerization, disproportionation, alkylation, polymerizations, Reforming and hydrogenation. Generally, the hydrocarbon feedstocks will contain less than 30 ppm Nitrogen and are in the presence of the catalyst. converted at the temperatures given above.

The catalysts prepared according to the invention are excellently suited for the conversion of a large number of hydrocarbons. For example, fluorinated platinized aluminum oxides are highly active in hydrocracking and hydroisomerization ν αϊ materials such as paraffins, slack wax and middle distillate oils at temperatures of 260-4-27 ⁰ C, pressures of 21-53 kg / cm and an LHSV (liquid hourly space velocity) of 1-20 in the presence of hydrogen. In general, catalysts with a lower fluorine content require higher conversion temperatures to achieve equivalent reaction rates. The selectivity for the isomerization of C ^ -C, - Mormal paraffins is improved at low temperatures. Aromatics can be hydrogenated and lubricating oil fractions altered in order to obtain a better viscosity index and pour point. Fluorinated aluminas containing metal compounds as oxides, e.g. . For example, the conversion of toluene to benzene and xylenes at 399-538 ⁰ C. The catalysts are active in the alkylation of aromatics and aliphatics and the polymerization of olefins at temperatures from 93 to 204 ⁰ G and pressures from 21 to 56 kg / cm ² . The fluorinated catalyst

- 10 -

109853/1895

BATH

are ren also active than the non-fluorinated mixtures, for example allows for hydrocarbon conversion at considerably lower temperatures a fluorinated platinum alumina isomerization of C ^ -CG-normal paraffins at 316 ⁰ C, while the non-fluorinated mixture at temperatures' below 427 ° C is inactive.

To illustrate the method according to the invention 'and its practical handling serve the following examples. -

Example I:

150 ecm. Commercial eta-aluminum oxide iait deposited on this Platinum (0.47% by weight) is calcined in air at 427 ° C. for 2 hours. Then 120 Grams of the calcined material in a reaction tube with hydrogen at the rate of 10 liters / hour reacted at 371 G. After the temperature was lowered to 3I6 G, 2 ecm was added. Heptacosafluorotributylamine every 15 minutes, up to a total of 16 ecm. Fluorination compound into the reactor were given. The gas leaving the reaction tube contained steam and was extremely acidic. Analysis of the fluorinated platinized alumina mixture showed one Flour content of 2.5% by weight.

The catalyst was then / pressure on its Isomerisierung- and cracking activity with a batch normal paraffin material having 10-14 carbon atoms, under conversion conditions of 343 ⁰ C, a LIIS "of 1, a hydrogen from

35 kg / cm and a ^ speed of 8.5 liters / hour. The product analysis showed that 41.8 % of the starting material were branched paraffins with 10-14 carbon atoms

- 11 -

BATH ORIGINAL

109853/1895

isomerized and 7.2% to hydrocarbons with less when 10 carbon atoms had been cracked.

Example II:

120 ecm. an eta-aluminum oxide mixture, on this deposited 0.4-7 Ge \ j .-% platinum, were calcined for one hour at 4-27 ⁰ C and then 10 ecm. Heptacosafluorotributylamine added. The fluorination component is adsorbed in the platinized aluminum oxide mixture by cooling in a closed vessel. The mixture was then transferred to a hydrocarbon conversion reactor for cracking and isomerizing a normal paraffin feed (see Example I). Using the process conditions of Example I and a catalyst activity at 34-3 ⁰ C was 0.6% Crackfraktbn with less than 10 carbon atoms and 6.8 ^c / o Isomerisierungsfraktion with 10 - 14 carbon atoms obtained. ^{The temperature was increased to 271 °} C. in order to increase the rate of activation. In the product analysis, the cracked fraction with less than 10 carbon atoms showed 1.9% and the isomerization fraction in the C ,, ^ G ^ jr range 30.6%. According to v. ^r Eiteren 6 hours gave the catalyst activity a 2.7% -Crackfraktiori with less than 10 carbon atoms and the isomerised fraction in the C ₀ -C ^ -.- area 35.1%. From the foregoing it can be seen that the process can be carried out in situ, ie in the hydrocarbon conversion reactor itself, and the increase in activity is related to the decomposition of the fluorinating compound in the presence of hydrogen, an active fluorinating species being formed under the in situ activation conditions.

Example III:

1000 ecm. Commercially available eta-aluminum oxide with 0.6% by weight Platinum was mixed with 50 grams of heptacosafluorotributylamine and placed in a pressure reactor with 7 ^

109853/1895 -12-

BATH ORIGINAL

Oxygen was squeezed off and heated to 288 ° C. Of the The reactor was left at this temperature for 1 hour and registered a maximum pressure of 17.5 kg / cm. In the pro- A product analysis found 3.8% chemically bound fluorine.

Example Df:

. 650 ecm. of a commercial reforming catalyst that 0.38% by weight of platinum on gamma-aluminum oxoid " with 26 ecm. Heptacosafluorotributylamine mixed and in given a pressure reactor. Oxygen was injected until a pressure of 7 kg / cm was reached, then followed Heating for one hour at 288 C ITs developed in approximately 3OOO ecm. large reactor a maximum pressure of 11.6 kg / cm. 4.3% by weight of chemically bound fluorine were found in product analysis.

Example V:

640 ecm. Commercially available eta alumina mixture containing 0.47 wt% platinum was mixed with 40 grams of heptacosafluorotributylamine and added to the pressure reactor. The oxygen pressure was stopped at 7 kg / cm and then ^{heated to 260 0} C for 1 hour until a maximum pressure in the reactor

of 14.1 kg / cm occurred. 3-7 wt% fluorine was present in the catalyst.

Example VI:

The catalysts of Examples III- V were used in the paraffin isomerization in order to maximize the oil yield with the lowest possible amount of cracked product. The properties of the starting material are given in Table I:

_ 13 _ ORIGINAL BATHROOM 109853/1895

TAEEULE I - starting paraffin -

API density 39.1

specific Weight 60/60 0.8285

Melting point ⁰ G 57.9

Oil content % 7.3

Sulfur %, less than 0.051

Nitrogen %, "x 0.10

n-paraffin % 53

average MG '408

The catalyst from Example III was in the isomerization above paraffin mixture at temperatures of 302 - 356 ° 0 used. Table II gives process conditions and the resulting products.

TABLE II ■ Reactor temperature ^{0 C} 302 , 3 316 329 356 Reactor pressure kg / cm 70 , 05 35.2 35.2 35.2 LIISV liter / liter-h 1 1.09 1.04 ■ 1.05 Hp-Ge se hw. Nm - ^ / m ^ 855 890 837 855 Yields (wt%) , 7 liquid product 97 99.1 99.6 96.5 stabilized " , 6 / based on liquid product 99 , 3 97.0 94.9 46.8 based on paraffin batch 97 , 7 96.1 94.5 45.2 Crack loss 2 3.9 5.5 54.8 stabilized product , 4 Melting point ⁰ C 57 52.9 51.5 27.5 % Oil content from the enamel points calculated 8th 22nd 30th 87 % oil content from the deparaffi • renation - - - 86.6

- 14 109853/1895

BATH

The data summarized in Table III represent the activity of the catalyst derived from Example IV.

TABLE I II

Reactor temperature ⁰ G 329 343 356

Reactor pressure 'kg / cm ² 35.2 .35.2 35.2

LHSV liters / liter · h 0.97 1.03 1.05

H ₂ speed Nm ⁵ / m ³ 926 872.5 855 yields (% by weight)

fl. product 96.0 95.5 38.3 stabilized product

based on liquid product 97.7 94.6 68.1

based on paraffin batch 93.8 90.3 60.1

Loss of cracking 6.2 9.7 39.9

Melting point ⁰ C 55.3 49.3 42.5

% Oil content calculated from the

Melting points 13 42 66

% oil content "from the

Dewaxing - 36.9 64.1

% Oil formation from the oil content calculated from the melting points 4 33 35

% oil formation from the oil content from the

Dewaxing - 27.3 32.9

Testing of the catalyst prepared according to Example V gave the values in Table IV:

' TABLE IV

Reactor temperature ^{0 C.} 343 356 371

Reactor pressure kg / cm ~ i> 3-, 2. 35.2 35.2

LHSV liters / liter-h 2.5 2.5 2.5

H ₂ speed NmVm ⁵ 766 766 766

- 15 10985 3/1895

BATH ORIGINAL

Yields (wt%)

fl. product 28 4-7 4-7

Loss of cracking 12 22 37

\\ ie can be seen from the tables, have the Catalysts prepared in Examples III-V 'have considerable activity for paraffin isomerization by Paraffin feedstock is converted into more liquid products that are important as lubricants.

From the foregoing, there emerges a significant method of making catalysts that are involved in conversion of hydrocarbons are useful. The catalysts are particularly biachable in the isomerization isomerizable Hydrocarbons, especially paraffinic hydrocarbons in the CLq-C,! ^ Range. The catalysts can in alkylation processes without changing the process conditions, to adjust the catalyst can be used. The process can be carried out in situ, e.g. B. in the coal-hydrogen conversion reactor itself, can be carried out without a prior transfer of the catalyst the activation reactor to the hydrocarbon conversion reactor must be done with the risk of getting wet. Also can be the process of regenerating an exhausted Catalyst can be used by heating the exhausted catalyst in air or oxygen to create the catalyst to decarbonize and then to treat in the manner described. The procedure works without the insert expensive chemicals, high pressures or temperatures and is therefore suitable for an economically working person Plant suitable. The catalyst can be any of the metals mentioned, e.g. B. platinum, palladium, ruthenium and rhodium included, where the selection depends on the operator, the

- 16 109853/1895

BATH ORIGINAL

- .16

Availability of the metal e.t.c. is dependent. Activation of the catalyst material occurs essentially independently of the type of metal mentioned. The process conditions to be changed do not differ significantly with the respective metal.

BAD ORfG / NAL

17 -

109853/1 895

Claims (12)

0? 71 027 (D 71) patent claims 1. A process for the production of a catalyst consisting of a hydrogenation component, an aluminum oxide and about 0.5-15% by weight of fluorine, characterized in that an aluminum oxide is mixed with a hydrogenation component consisting of those in groups VI B and VIII of the PSE existing metals, compounds of these metals or mixtures thereof, with a mixture of hydrogen or oxygen and an organic fluorine compound having 2-16 carbon atoms is reacted at a temperature of about 93 649 ⁰ C. 2. The method according to claim 1, characterized in that indicates that an aluminum oxide with a proportion of 0.01-30.0% by weight (based on the Metal) hydrogenation component is used. 3. The method according to claim 1 or 2, characterized in that an aluminum oxide with platinum, palladium, ruthenium, rhodium, nickel, cobalt, molybdenum, chromium or tungsten, a combination of these Metals or a mixture thereof as a hydrogenation component is used. BATH 109853/1895 -18- 4. The method according to claims 1-3 »characterized that an aluminum oxide with platinum, palladium, rhodium or ruthenium or a Compound of these metals or a mixture in 0.12.0 wt .-% Catalyst weight is used as the hydrogenation component. 5. The method according to any one of the preceding claims, characterized in that an organic fluorine compound with the general formula ° n ^P a ^H b ^X o - where X = nitrogen or oxygen, η = 2-16, a = 1 to 2 η + m, b = 0 to 2n + m-1, c = 0 Ms 1, as well as m = 2 (if c = 0 or X = oxygen) and m = J (if X = nitrogen) mean, for fluorination is set, 6 «Method according to one of the preceding claims, characterized in that the organic fluorine compound heptacosafluorotributylamine, Hexafluoroethane, hexadecafluoropropyltetrahydropyran or hexafluoroacetone can be used. 7. The method according to any one of the preceding claims, characterized in that with a hydrogen: fluorine compound ratio of 0.5-100 gram-moles Hp / gram-atom fluorine, preferably 2- 10 gram-moles Hp / gram-atom fluorine. 8. _ Method according to claims 1-6, characterized in that - - 19 - 109853/1895 BAD ORiaJNAL 19 - indicates that having a relationship of oxygen: fluorine compound of 1-50 gram-moles Oo / gram-atom carbon of the fluorine compound, preferably 2-10 gram-moles 0 o / gram-atom C of the fluorine compound., is treated. 9 · Method according to one of the preceding claims, characterized in that the treatment is carried out at 232 - 4-82 ° C. 10. The method according to claims 1-6 and 9? characterized in that with the use of oxygen at 260 to 371 ⁰ C treated v / ith. 11. The method according to any one of the preceding claims, characterized in that Fluorine from 0.5 - 6.0 wt .-; <> introduced into the catalyst will. 12. The method according to any one of the preceding claims, characterized in that an aluminum oxide such as eta-aluminum oxide, gamma-aluminum oxide, Si0 ₀ aluminum oxide or an aluminosilicate, preferably with eini
is treated. preferably with a surface of 50 - 400 m / gram, 13 · Vervendung of the catalyst prepared according to any one of the preceding claims in the hydrocarbon conversion of hydrocarbons at 93-538 ⁰ C j η presence of hydrogen. BAD OBiGINAU 109853/1895