DE1568259C - Process for the catalytic allyl alkylation of hydrocarbons - Google Patents

Description

1 2

Under "allyl alkylation" in the present (2) about 7 to 45 ecm of an inert, oxygen-containing

Registration of the 1,2-addition of an alkali metal inorganic solid, which is a partial

allyl carbanions (e.g. particle size between 0.1 and 10 microns

CH ₂ = CH-ΟΗ ₂ ΘΜΘ, ₅ ^ _about ' ₇ . ₁₀ _4 _to i _{) 0} . lO-i moles _a r up to

where M is an alkyl metal cation) to the at least 230 ° C heat-resistant organic

Double bond of a monoolefin are understood to be a connection with a dipole moment of min-

where a proton exchange takes place, at least 1 Debye unit (μ i 10 ¹⁸ esu) and min-

by an olefinic alkylate and a new alkali-Ütesting an oleophilic group and

metal allylcarbanion ion pair is formed (H. io (4) about 0.3 to 7.5 liters of an aprotic carbon

Pines and V. Mark, JACS., 78, pp. 4316 to 4322 Hydrogen,

and 5946 to 5950). . "

For the allyl alkylation of hydrocarbons, under dispersing conditions and at a temperature. B. for the dimerization of olefins, Co-Dimeri- door below about 230 ° C in an aprotic carbonation of dissimilar olefins, side chain alkyl 15 hydrogen medium has been produced.
lation of aromatic compounds and the like. excellent effectiveness and high repro alkali metal-containing catalysts for this allyl alky- ducibility. The induction times, which are chemically extraordinarily reactive, should be achieved when they are used, are insignificant or capable and in the inert hydrocarbons, with a short duration, and the coke and tar formation products they are used are essentially insoluble in the hitherto customary catalysts as well as the Be hh. Due to these properties, no catalyst metastability is eliminated. Effective allyl alkylation catalysts are known, particularly advantageous in the process according to the invention is the elimination of the long mechanical life otherwise required for continuous allyl alkylation processes, combined with high mixing. In general, a monomer gas nozzle effectiveness is exhibited. It is known that an allyl stream or an inert gas stream are applied.
alkylation catalysts using small suitable processes for the production of the quantities of organic dispersing auxiliaries produced. Catalysts used in the invention are provided which provide improved catalysts. Subject of patent 1269 598. In general, these systems have proven in practice, however, as 3 ° comprises the production of satisfactory allylalkyliemeta-stable. That is, small deviations or the bringing together of ge-fluctuations in the reaction conditions can cause molten alkali metal, separately sorted solids, rapid agglomeration of the disperse phase particulate matter, a polar organic compound. Another noticeable effect that cannot be predicted in an aprotic hydrocarbon medium is an autokata under dispersing conditions. Mixing is used in lytic tar and coke reaction, e.g. B. carried out between temperatures of about 30 to 230 ° C, see the · dispersant, the catalyst-active reactants during the preparation of the catalyst complex and possibly the Me- temperatures just above the melting point medium. If any of these conditions apply, the alkali metal up to 20 to 40 ° C above the melting point of the reactor, process lines and the like must be preferred, since mutual stabilization is required until the complex, which is carefully cleaned and operation is started from the beginning will. In the production of allyl alkylation effects of the mixed constituents, it is advisable not to affect the active one. Higher temperatures can therefore be used to deposit catalyst material on a solid, but offer only little or overdevelopment. Depending on the solid, this cannot be an advantage at all. The inorganic solid oxy used, for some improvement in the counter-compound, must lead to an extremely fine particle size over the dispersed system. Nonetheless, that is, generally below about 10 microns, these catalysts tend to move below and above about 0.10 microns. Aggregate particle sorts in allyl alkylation conditions; To counteract this phenomenon, range from 0.1 to 6 microns is excellent, mechani- 5o catalysts. Solid particles with sizes slightly above mixing with considerable energy and appearing 10 microns - as the microscopic expense required. These secluded. Investigation shows - no catalyst complex Catalysts show as a result of undesired secondary formation. On the other hand, particle size reactions are often of limited life and below about 0.1 micron are unsatisfactory,
because of unpredictable deviation during 55 The inorganic oxy-compound envisaged for use in the production of the catalyst which has a different effectiveness in its production from one batch to another. 'Fertilizers are generally not acidic and reactive. It has now been found that the catalytic allyl ren even in extremely finely divided form in the substantial alkylation of hydrocarbons in the presence do not ^borrow successfully with alkali metals at temperatures up to an alkali metal-containing catalyst 6o to 200 ° C and even 230 ° C or more. It is also carried out if the reaction does not react with hydrocarbons until the presence of a catalyst, which by combining 230 ° C and more and expediently have a mixture of the following components in the specified density below 5.0 g / ccm . In a preferred form nen proportions: ^sm d this oxy compounds krastallin and have

65 a density below 3.0 g / ccm. Oxy-

(1) 1 gram atom of molten alkali metal, which compounds in the form of crystalline oxy salts suitable

Sodium, potassium, rubidium or cesium or especially oxy salts, in which the negative remainder

is a mixture thereof; Contains elements with atomic numbers below 17; of the

Oxysalts, in which the negative remainder contains elements with atomic numbers below 17, are suitable on best the compounds in which the positive residue of the cation of an element is related to one Exhibits electronegativity below about 1.6 (see "Nature of the Chemical Bond", Linus Pauling, Cornell Univ. Press, 1945, p. 65). Oxy compounds are understood as meaning both individual compounds also mixtures of compounds.

Functionally, the suitable solid inorganic compounds (1) must have bound oxygen contain, (2) essentially do not react with alkali metals, (3) a particle size in the range of about 0.1 to 10 microns and (4) free of relatively loosely bound or adsorbed Be water.

A wide variety of organic compounds can be used for the preparation of the catalyst complex, as long as they have a considerable dipole moment and are essentially heat-resistant up to about 230.degree. They must therefore contain at least one non-reactive olephilic group. The dipole moments of the organic compound preferably correspond to at least 1 Debye unit, in particular over 1.5 units and even up to 5 units. The non-reacting oleophyl constituent of the organic compound must be an inert hydrocarbon radical, which can consist of a single methyl group, but expediently consists of one or more non-reacting hydrocarbon radicals which contain four methylene-CH., - units or more, as in alkyl- , Cycloalkyl, 'alkenyl, cycloalkenyl and alkyl-substituted cycloalkyl and phenyl radicals with up to 20 carbon atoms per group and more. The use of organic compounds with a higher molecular weight and in particular compounds which are relatively insoluble in paraffinic white oil-petroleum fractions does not result in any particular advantage. Particularly preferred organic compounds useful in the process of the invention have a dipole moment of at least 1 Debye unit; they have a single polar constituent group and fewer than three non-reactive oleophylic hydrocarbon groups, each of which has about 1 to 20 carbon atoms . the best results are organic compounds containing a single acidic polar group with a pKa in the range of about 1 measured to 28 (in the ^coal; hydrogen medium or qualitatively determined a pKa in the range from the pKa of benzenesulfonic acid as an extreme value at the one side and the only less »lower pKa der« -hydrogen is limited by toluene on the other side), and contain a single, non-reactive oleophyl group with about 1 to 20 carbon atoms the oxygen- and nitrogen-containing groups are preferred.

The intended polar groups include:

I. Strongly acidic (pKa range 1 to 8)

-SO ₃ H, -CO ₂ H, -PO ₂ H, -SO ₂ H, -PO ₃ H ₂ ; II. Medium acidic (pKa range ~ 9 to 20)

-OH, -SH, -CH, NO. "-CH., C = N, CHCHO (CH; CO)

l weakly acidic (pKa21 to 28) -NH ₂ , -CONH ₂ , -SO ₂ NH ₂ , -PO ₂ NH ₂ .

Functionally, it is believed that the polar nature of the group acts in part as a bonding force serves, which by electrostatic interactions. gene with the solid oxy compound for the stability of the Contributes to the catalyst complex. It is assumed that chemical interactions also play a role - hence can be part of the alkali metal with the polar organic compound in the preparation of the complex react to produce a salt. '_. ίο True, the materials listed above preferred as polar organic material as it has the more suitable allyl alkylation catalyst systems appear to result, but the derivative forms are also suitable. For example, salts of the acidic organic polar materials are useful, but generally have the disadvantage that they are relatively difficult to achieve the desired distribution of these materials in the catalyst complex leaves. Other and more suitable derivative forms than the salts are the esters and ester-like forms such as ethers, anhydrides, peroxides, acetals and ketals which are oil soluble and with a portion of the catalyst feedstock and active material react and can be converted into forms which correspond to those obtained when using the

acidic materials are produced as such. "

The catalysts suitable for preparing the catalysts used in the allyl alkylation according to the invention Alkali metals are sodium, potassium, rubidium and cesium and their mixtures; i.e. H. Alkali metals with an atomic number below 56 and above 3. Lithium alone proves ineffective and appears in mixtures with other alkali metals contribute little or nothing to the effectiveness, · see above-35. as far as allyl alkylations are concerned; Potassium, rubidium and cesium are more suitable, and Potassium is clearly superior, the active component of the catalyst complex can come from the alkali metal hydride or a corresponding organic metal derivative, provided that the ■ Particle sizes are approximately 1 to 10 microns. "

The continuous hydrocarbon phase used in the manufacture and use of the allyl alkylation catalyst complexes is required, can be made from a normally aprotic, inert hydrocarbon, usually a refined paraffinic hydrocarbon that is free from trace amounts from impurities from partial oxidation, or from reactive aromatic alkyl hydrocarbons and conjugated diolefins. Suitable hydrocarbon media have when measuring in a 1 cm cell, an absorbance at 275 niu less than 0.3. In general and to facilitate the use of the allyl alkylation catalysts in continuous processes the hydrocarbon medium is usually selected so that its boiling point exceeds that of the Allvlalkylierunnsproduktes. This will make the most desirable distance of the vapor phase product from the reaction zone.

By non-reacting inorganic solid oxy compounds are meant inert compounds, which bind little or nothing at all of the total amount, e.g. of the alkali metal, if the extremely finely divided solid into an inert hydrocarbon under a nitrogen or other inert gas atmosphere is brought. Due to the extraordinary reactivity of the allyl

The amount of polar organic compound which can be used per gram atom of alkali metal to prepare the allyl alkylation catalyst complex varies as it depends in large part on molecular weight. High as up to 1.0 x ΙΟ ^"1 mol, and even only 7 x 10 ~ ⁴ mol of the organic compound can be used. When the molecular weight is high, and such. Is located in a region about a C ₁₀ carboxylic acid

[C ₉ H ₁₉ (COOH)]

or corresponds to a higher acid, smaller amounts of the compound are expediently ver

carry. An extremely fine connection which passes this test proves to be sufficiently inert to it the allyl alkylation catalyst, so that satisfactory catalyst complexes can be achieved,

In general, the oxygen-containing inorganic ones Compounds, which are sometimes referred to as "oxy compounds" in the following, their cationic constituents elements with relative

including about 2.5 " ^{· 10" 3} up to about 1 · ΙΟ " ¹ mol of the polar organic compound per gram atom of alkali metal used. In general, therefore

Al.kylierungskatalysatoren compared to a large number of different agents and also due to the z. Currently little physico-chemical knowledge, with regard to the reactivity between> the extremely finely divided solid compounds and the active catalyst itself is an empirical stability test useful to the meaning of "unresponsive" in the context of the present Define invention. After this attempt, an unresponsive compound is understood to mean io that compound which after 2 hours of contact at 150 ° C with an alkali metal, e.g. B. Potassium, upon reaction with 2-methoxyethanol, at least 65% of the expected hydrogen, based on the used

dete amount of metal results. In the attempt you have to turn 15. In general, therefore amounts are necessarily the particle sizes 0.1 to 10 microns loading 1.4 x 10 ^-2 mol / gram atom of compounds having

Molecular weights which are greater than those of C _{10 carboxylic} acid are unsatisfactory and represent a problem with which a significant increase in viscosity is associated. For these materials, about 2.5 · " ³ up to 1.0 · IO-2 mol / gram atom alkali metal is particularly useful. On the other hand, the preferred range for the lower molecular weight polar organic compounds having electronegativity values below 1.6 is not particularly suitable cations are lithium, for example, that of a C ₉ carboxylic acid C ₈ H ₁₇ (COOH) and thium, sodium, potassium, rubidium, cesium, beryllium, magnesium , Calcium, strontium, and barium
Aluminum either alone or mixed with oxygen-containing inorganic compounds, which as 30 about 7 · 10 ~ ⁴ up to 1.0 · ΙΟ " ¹ mol of the polar organianionic constituent orthosilicate, metasilicate, see compound per gram atom of alkali metal and carbonate or sulfate, which in the essentially about 7 to 45 ecm of the very finely divided Oxyverbin are free of loosely bound water.Depending on the shape, dung required to produce a stable allyl alkyl origin and pretreatment can produce this material catalyst. While the above materials for use in the production of the 35 The description refers to carboxylic acids, the allyl alkylation catalyst complex may or may not have substantially the same relative values used finely divided silicon ox yde in the test as When carrying out the method according to the invention

exceptionally reactive and not very useful when using the above-described cambodies have proven. Neither can the catalysts remain the reaction chamber and catalyst Predict behavior of aluminum oxides without significant pollution. This is confirmed by the are of different origins. The above test results in the following experiment:

feit a positive and reliable means of fest- According to the instructions of Example 7A of the German

provide new, suitable, solid oxy compounds for 45 patent specification 1,269,598, an allyl alkylation was prepared for use in the decay catalyst according to the invention using a mixture of allyl alkylation catalysts for sodium metal and potassium metal in a weight ratio of 24: 1. For the production of the catalyst, 6.25 g of the alloy, 75 ecm of the para ratio to the molten alkali metal or aluminum hydrocarbon, 0.3 ecm of oleic acid and potassium metal mixture fluctuates within a certain 6 g ball milled talc with a th range. In general, the net solids particle size used is 0.1 to 10 microns, about 7 to 45 cubic centimeters by volume of finely divided solids. The finished catalyst was required along with 74 grams per gram atom of the alkali metal. A butene-1 and 25 g Athens in an advantageous range of 600 ecm is around 10 to 36 ecm 55 oxygen-free dry autoclave introduced. The solid, in particular about 12 to 20 ecm. Depending on the autoclave and its contents, shaking the. Density ■ of the corresponding oxy compound during the heating time and the subsequent temperature fluctuates, of course, when the action time to be used is heated to 150 ° C. As soon as 150 ° C softens. If the relative amounts of the solid content were much smaller, the reaction of the feedstock continued leading to the formation of metastable grains. The maximum pressure was 73.15 kg / cm ² , which did not plex or not to complex at all. Relative
Amounts of the solid greater than about 45 ecm
do not seem to provide a substantial gain in stability

to effect the Allyialkylicrungskoinplexes; this is

The lowest pressure was 43.75 kg / cm ² , and the total reaction time was 103 minutes.

The cooled autoclave and its contents were purged with nitrogen gas in order to

even undesirable because the presence of unnecessary 65 hydrogen and the catalyst was removed like inert solid in the reactor necessarily examined. The autoclave was perfectly clean, he a corresponding reduction in the reactor output contained no traces of tar, coke or free additive Volume unit means. . aggregated material.

The. The appearance of the catalyst was excellent, "it consisted of a slightly red-brown slurry. Microscopic examination showed that the catalyst had a particle size of 3 to 15 microns exhibited. ■■ · ■ '.

In order to also show that, according to the process according to the invention, alkylbenzenes, which are normally not for use in alkylarylbenzoisulfonate detergent manufacture are easily converted to those of useful molecular weight the following experiment was made:

In a shaking autoclave, an HF-alkylation alkylbenzene obtained from benzene with a heat cracked wax olefin along with Athens and a potassium-containing allyl alkylation catalyst brought that according to the following Example 1 using talc and oleic acid was manufactured under the following conditions:

Pressure, atmospheres 62 to 35

¹ temperature, ⁰ C 150

Time, hours 1.7

After consuming about 0.5 moles of Athens per mole of the alkylbenzene feed, the reaction proceeded set. Examination of the product showed that the catalyst complexes used according to the invention were found especially for the improvement of alkylbenzenes with at least one α-hydrogen (CHRjR.,) Are suitable, the molecular weight of the alkyl group of an alkylbenzenes by at least one Ethylene group is increased. That way, can one is the alkylbenzenes produced from low molecular weight olefin fractions, which are normally unsuitable for use in alkylarylbenzenesulfonate detergent manufacture are easily converted into a substance with a useful molecular weight using the method according to the invention convert, so that alkylbenzenes with side chainsii with 12 to 16 carbon atoms are produced be able.

B e i s ρ i e 1 1

(A) Following the procedure of Example 7A of German Patent 1,269,598, sodium, commercial talc (1 to 10 microns), oleic acid and white oil in the amounts of 1 gram atom, 8.3 ecm (24 g), 3.2 -K) - ³ MoI and 0.2 liters at 120 ⁰ C in a catalyst complex converted. Part of the catalyst, 58 g or 65 ecm, was made by addition

ίο diluted by 35 ecm of oil and introduced into a shaking autoclave together with 66 g propene "and 36 g ethane. After about 90 minutes at 150 ° C. and 90.3 kg / cm ² the reaction began, which was indicated by a drop in pressure. The reaction was stopped at a final pressure of 47.6 kg / cm ² , and 50 ecm of a product with the following composition were obtained:

1-pentene 6% ■ -

2-pentene .. 66%

Methyl pentenes 3%

Heptene 16 "/ <■

Other fabrics 9%

(B) A part of the catalyst in (A), which contained 4 g of sodium, was together with 150 ecm Toluene and 35 g of ethane introduced into the autoclave. The autoclave and the contents were at 10 hours Maintained 150 ° C. The product obtained boiling over toluene (53 ecm) consisted of the following substances:

^ Aromatic hydrocarbon

(assumed n-propylbenzene) ....... 81 "/»

C ₁ aromatic hydrocarbon

(assumed 3-phenylpentane) ....... 18%

Other substances .................. '1

In contrast, attempts to effectively dimerize propene have been made using it of sodium metal, which on finely divided (over 100 microns) inert materials in an inert hydrocarbon slurry deposited in the absence of polar organic compounds unsuccessful. This can be seen in the following table:

Reactions of propylene with a supported sodium catalyst

Conditions of the operation

Weight percent added Na

temperature time ' ⁰ C hours 232 16 150 24 150 8th 150 18th 150 24 150 15th 204 17th 204 7th

Results

Powdered Na ₂ CO ₃
Quartz sand .............

Kappa clay .......

Celite + Anthracn ...
Molten clay

Kappa clay

Celite 408

Alpha Alumina ......

10

3.2 o / o K

0.8 »/ ο Well

4.9 36

5.4

20 13

Minor response

slow reaction, tarry product

Traces of the product

no reaction

no reaction -

Traces of the product

no reaction

no reaction

The experiments described above showed that the sodium metal hall catalysts were

in the allyl alkylation according to the invention using calcium carbonate and oleic acid and

If the sodium metal-containing catalysts achieved results comparable to those in (A). Besides that

The following other Olelin ReaUlion pairs have significantly improved performance compared to the previous ones

common catalysts showed. Scored in the same way: (a) Athens and 1-butene and (b) Athens and

109 683/147

Isobutene. As in the case of the calcium metal-containing catalysts the coke and tar making problems appeared to be eliminated.

Example 2

A potassium rivet allylation catalyst was like in Example I using metamorphic talc and oleic acid. A lot of 35 ecm (which contained 2 g of potassium) was diluted to 100 ecm with white oil and placed in a small autoclave with 63 g of isobutene and 72 g of Athens introduced; the autoclave and its contents were heated. The reaction started as soon as the temperature reached 112 ° C, and was completed after a reaction time of 12 minutes. As the gas-liquid chromatographic analysis showed the product had the following composition:

2-methyl-1-pentene 31%

2-methyl-2-pentene 11%

C _s -olefin 43%

ίο

13.4 cm (39 g) talc and 5.5 x 10 "» moles of oleic acid Bred alkylation catalyst in contact and in a 3.8 liter autoclave with stirrer introduced, which 36 g of catalyst (18 g of K) about 1000 g of paraffinic white oil, 560 g of 1-butene and Contained 240 g of Athens. The reaction started when the heated mixture reached about 70 ° C. To After a reaction time of 20 minutes, the reaction was essentially complete. The final temperature was 138 ° C, and the pressure fluctuated between 44 and 28 atmospheres. The product had the following composition:

3-methyl-1-pentene ..: ....., 82

3-methyl-2-pentene ..... 3

x-n-hexenes 5

12%

Other fabrics 3%

Similarly, 74 g of propene and 47 g of Athens were obtained in the presence of a second portion of the potassium metal containing Catalyst brought into contact with one another at 115 ° C. The won product contains 75 ecm of a mixture of the following components:

1-Peiiten. 70%

2-pentene 26%

.c-methyl-pentenes 4%

In the above examples, the reaction products and the autoclaves were free from carbonaceous Deposits, and the catalysts used were highly active and suitable for effective continued use in a continuous reaction vessel. The unusually low Reaction exit temperatures are also indicative of the quality of the inventive Process made allyl alkylation catalysts. ν,

Example 3

An allyl alkylation catalyst was prepared using the procedure of Example 1, but in this case the oxy compound used was sodium metasilicate instead of talc. Approximately 8 g of the catalyst complex in 100 cc of white oil and 11.3 g of propene were introduced into a 630 cc shaken autoclave-making ". After a short time at 150 ⁰ C, the reaction started and was continued for 4.3 hours, with the pressure of 88.2 dropped to 42 kg / cm ^2. The reaction was stopped by cooling and the product was recovered The catalyst used was examined microscopically and found to consist of particles ranging from 1 to 15 microns.

The product had the following composition:

4-methyl-1-pentene ....... 79%

4-methyl-2-pentene 10%

η-witches 9%

Other fabrics 2%

Example 4

1-butene and Athens were with that of Example 1 using 1 gram atom of potassium, C ₈ alkenes

10

Example 5

The above example was repeated, but in this case the temperature was maintained at 83 ° C. Under these conditions the reaction time was 150 minutes and the 3-methyl-1-penteii fraction was 85.3%.

As indicated in Examples 4 and 5, the catalysts used in the process are of the present invention Invention used, particularly effective for the production of 2-methyl-L-pentene. If the. Reaction is carried out in a continuous process and preferably about If 10 to 80% conversion is caused per operation, the product can be used at reaction temperatures in the range from 80 to 200 ° C and higher, at pressures in the range from-K) to 200 atmospheres and liquid roughness velocities-from 0.2 to 200 / hour Comprise 90% 3-methyl-1-pentene.

Example 6

If you have 1-alkenes with higher molecular weight brings into contact in the presence of the catalyst complex as in Example 4 and 5, takes place alkylation is easy, but somewhat higher temperatures should advantageously be used. For example, at about 150 ° C the reaction occurs easily, and about 10 g of Athens per gram of the potassium used in the production of the catalyst are consumed per hour when Deceit-1 Is used. The composition of the product can vary depending on the ratio of the starting materials sway a little; it corresponds roughly to the following composition:

Decene 9.3 mole percent

Dodecene 76.8 mole percent

C _U H., _S 10.3 mole percent

-. ■ ·.

The alkylation catalyst is therefore suitable for the improvement of 1-alkenes and in particular from olefins in the non-cleaning range to olefins of higher molecular weight which the have the molecular weights required for the manufacture of cleaning agents. 1-alkenes with 3 up to 20 carbon atoms per molecule can be converted into olefins, which have a molecular

have an increase in weight of 1.2 and even 3 ethylene unit attachments.

Claims (1)

Claim: Process for the catalytic allyl alkylation of hydrocarbons in the presence of an alkali metal Catalyst, characterized in that the reaction takes place in the presence of a catalyst which is produced by bringing together the following ingredients in the specified proportions: (1) 1 gram atom of a molten alkali metal, the sodium, potassium, rubidium or is cesium or a mixture thereof; (2) about 7 to 45 ecm of an inert, oxygen-containing inorganic solid having a particle size in the range of about 0.1 to 10 microns; (3) about 7 · 10 "* to 1 · ΙΟ" ¹ mole of an organic compound having a pKa in the range of about 1 to 28, a dipole moment of about 1.0 to 5.0 Debye units, and one to three olephilic groups having 1 to 20 carbon atoms per group; (4) about 0.3 to 7.5 liters of a normally aprotic hydrocarbon, under dispersing conditions and at a temperature below about 230 ° C, in an aprotic Hydrocarbon medium has been produced.