DE1443543A1 - Process for the preparation of a detergent alkoxide - Google Patents

Description

our sign ρ 3306/64 HAMBURG, den HAMBURG * /

AFFECTi

! Marriage to British Petroleum Company Limited, London, England

Process for the preparation of a detergent alkoxide

The invention relates to the preparation of a detergent alkoxide .

Detergent alkylates made from propylene tetramer have been used to make sulfonate detergents to manufacture. However, such detergents are not easily converted by aquatic organisms and you is generally believed to be due to the highly branched nature of the side chain derived from the propylene tetramer, is due. It has now been found that a cleaning agent alk ^ lat from propylene by a two-step dimerization process can be made to a detergent olefin fraction to create which then with an aromatic

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Hydrocarbon is condensed. The detergent alkylates produced can be sulfonated in a conventional manner to give a product that is more easily passed through sewage organisms than the usual detergents used by propylene tetramer come.

Accordingly, the present invention provides a method created for the production of a cleaning agent alkoxide, that consists in that propylene is dimerized in the presence of a catalyst which consists essentially of cobalt on a Carrier is made of activated carbon to form a product containing a substantial proportion of n-hexenes from the product a fraction which consists essentially of n-hexenes is separated off, this fraction is dimerized in the presence of a catalyst and a fraction of the second dimerization product in the range of the number of carbon atoms of C. q - C-. G is condensed with an aromatic hydrocarbon in the presence of an alkylation catalyst.

The catalyst which is used to dimerize the propylene can be prepared by impregnating the carbon support material, e.g. coconut charcoal or "Ultrasorb" charcoal, with a solution of a decomposable cobalt salt, e.g. the formate carbonate, but preferably the nitrate, the salt is decomposed to the oxide by heating to an elevated temperature and then the oxide is reduced by treatment with hydrogen;

In contrast to catalysts, which were previously proposed for the dimerization of propylene, to produce straight-chain hexenes to yield, e.g. transition metal oxides, such as nickel oxide, on carriers, like silica, silica gel, or cracking catalysts

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of silicon dioxide / aluminum oxide, the above cobalt catalysts on a carrier, which are used according to the invention, have the advantage that they have greater selectivity for dimer production and the proportion of n-hexenes in the nexe ^ r ^ tion is significantly higher.

Likewise, the proportion of 2-methylpentene-2, which is present in the Hexenprodukt.vorhanden, is very much lower than when metal oxide catalysts can be used on a carrier. This is beneficial because this particular methylpentene is heavier of the linear hexenes as other methyl pentenes, such as 4-methylpentene-2, and if it remains in the fraction which the is subjected to the second stage of dimerization to a great extent branched dodecenes, which is a disadvantage for the production of a biologically mild detergent.

The catalysts can contain a wide range of cobalt concentrations, but generally contain 1-30 Gew # cobalt; for example 10-20 wt. is very suitable.

The first dimerization stage is preferably carried out at a temperature in the range 20-200 G, in particular in the range 30-50 C under sufficient pressure to keep the reactants in the liquid phase. Suitable pressures are 21-70 kg / cm ² , for example about 42-49 kg / cm ² .

The cobalt catalysts used in the first dimerization stage are to some extent supported by sulfur compounds, Carbon monoxide, oxygen and acetylenes are poisoned and should therefore be used to maximize the use of the catalyst Propylene feed essentially free of such compounds

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be. Although pure propylene is a desirable feedstock is, a fraction containing propylene, e.g. a C, fraction, obtained by catalytic cracking of hydrocarbons or by steam cracking or thermal cracking will be used as feed, preferably after acetylenes and dienes have been removed therefrom, for example by selective hydrogenation. Propane does not adversely affect the catalysts and therefore can be present in the feed stream. The first dimerization step can be carried out in such a manner be that the selectivity for dimer formation exceeds $ 90 and such that the n-hexenes are approximately 55 wt of the products of the first dimerization stage becomes a fraction consisting essentially of n-hexenes by known methods using for example molecular sieves, urea adduction or preferably fractional distillation, separated. It can be implemented Recovered propylene and sent to the dimerization stage to be led back.

The fraction, which consists essentially of n-hexenes, is in a second stage in the presence of a catalyst dimerized. The catalyst can be a transition metal oxide be that on a support, for example silicon dioxide or Silicon dioxide / aluminum oxide, e.g. manganese oxide on silicon dioxide / aluminum oxide. The preferred catalysts which are used are catalysts of the 7.iegler type, which are advantageous by the inclusion of, for example, one Borane, such as a trialkylborane, or by the addition of

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Copper or a transition metal of groups 3 to 8 of the Periodic Table or their reducible compounds modified can be.

Suitable catalysts of the Ziegler type are hydrides of beryllium, aluminum, gallium and indium and derivatives thereof Hydrides in which one or more of the hydrogen atoms of the Hydrides are replaced by alkyl or aryl radicals. The preferred Ziegler-type catalyst is an aluminum trialkyl, e.g. Aluminum tri-n-hexyl.

The reaction conditions for the second dimerization stage are similar to those used in the first stage, ie temperatures in the range 60-250 ^° C. and pressures sufficient to keep the reactants in the liquid phase, although higher pressures up to about 2000 atmospheres can be applied.

_{A fraction in the carbon number range C 10} to C r is preferably separated off from the products of the second dimerization stage by fractional distillation. This fraction contains dimers of η-hexene and it is preferred that the distillation of the dimer product is carried out so that the fraction recovered consists predominantly of such dimers, ie the fraction consists predominantly of CLo-olefins.

The C <jq ~ ^ 16 olefin fraction obtained is then treated with a aromatic hydrocarbons, e.g. benzene, xylenes or naphthalene, preferably benzene, in the presence of an alkylation catalyst, such as aluminum chloride, boron trifluoride or anhydrous hydrogen fluoride, condensed. The condensation is preferred

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in the liquid phase at a temperature in the range -20 100 C executed. Bas alkylation product is after. separation of the catalyst is fractionated to unreacted aromatic hydrocarbon for recycling, a small amount of a light alkylate fraction and a distillation fraction of a cleaning agent alkylate to win, with a small amount of heavy alkylate remaining as a residue.

The distillate of the cleaning agent fraction is in usual Way, for example, sulfonated using sulfuric acid or sulfur trioxide and the sodium salts by neutralization of the sulfonic acids formed.

The following example illustrates the present invention.

example

(A) This illustrates and shows the first stage of dimerization the advantages of using cobalt as a catalyst on an activated carbon carrier compared to nickel oxide on silicon dioxide-aluminum oxide.

Propylene was in the presence of the specified catalyst and dimerized under the conditions given in Table I below. The product distributions in the hexene product are given and it can be seen that when the cobalt on charcoal catalysts are used, not only is greater selectivity for total hexenes is present, but also the proportion of n-hexenes in the total hexene product ib% greater and the amount of 2-methylpentene-2 produced is very much reduced.

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Table 1 catalyst Nickel oxide /
Silicon 2 Cobalt / charcoal 4th dioxide / aluminum
minium oxide Attempt no. 1 3 Reaction 70 50 dinsunsen 43 · 46 Temp. ⁰ O 70 610 40 660 Pressure, kg / cm 49 66 42 93.5 psig 700 600 Gew # Hexene in the product 53 1.8 91 1.2 Witch product distribution 7.6 14.0 Witches-1, Wt $ 1.4 15.0 1.3 35.2 Witches-2 (ice) 8.1 0.8 15.1 1.2 Witches-2 (trans) 16.9 3.3 31.0 6.2 Witchη-3 (ice) 1.0 9.2 1.4 1.9 Witches-3 (trans) 4.7 9.1 6.3 8.3 4-methylpentene-1 .6.0 32.3 2.4 24.5 4-methylpentene-2 (ice) 8.7 11.6 9.9 23 4-methylpentene-2 (trans ) 32.7 1.8 26.7 3.2 2 ~ methylpentene-2 11.0 - 2.4 - 2-methylpentene-1 1.6 0.4 3.4 - 3-methylpentene-1 - 0.3 - - 3-methylpentene-2 (ice) 0.3 0.7 - - 3-methylpentene-2 (trans ) 0.3 5.7 - - 2 ₁ 3-dimethyl butene-1 0.7 0.4 - 2,3-dimethylbutene-2 5.0 28.5 - 57.8 other 1 _f 6 18.8 _ 54.1 Total linear witches 32.1 55.1 $> linear hexes in
Total witches 17.1 50.0

The catalyst used in Experiment 1 contains "" Experiment 2 "» »

"" Experiment 3 "" "

dd

Attempt 4

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10.2 $ Ni and 1 3 $ Al ₂ O ₅ 13.5 $ Ni and 10.4 $ Al ₂ O

$ 17.9 Go on Ultrasorb

SC coal

$ 23.3 co on Ultrasorb Coal leached with dilute nitric acid ■ had been.

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(B) This illustrates the first stage of dimerization. A catalyst was made by adding steam activated coconut shell charcoal, which was washed with 10% nitric acid to bring the ash content below 1% by weight, with an aqueous one Solution of cobalt nitrate of sufficient strength to remove about 18> 'cobalt to result in the finished catalyst, was impregnated. The catalyst was in a rapid stream of preheated Nitrogen heated to 200 ° C, cooled and the catalyst bed saturated with water and finally heated to 270-300 ° G.

It became a feed item that consisted of $ 99.5 pure propylene, which was essentially free of dianes, acetylenes and sulfur compounds, in a 1 liter shaking autoclave pressurized with 10.2 g of the above catalyst to 42 kg / cm (600 psig) at 40 ° C and under for 5 hours kept these conditions. The products were placed in a cold trap condensed and propylene unconverted after evaporation, 341 g of a colorless liquid were obtained from which $ 92 were witches. 54 $ of witches were ^ linear witches. The liquid product was fractionated in a trimmed distillation column to make up one fraction - about $ 50 "of the total yield ^ which contained 98.8 $ linear hexenes. A complete Analysis of this fraction showed that it contained:

Witches-1 0.7 wt

Hexen-2 (cis) 27.4

Hexene-2 (trans) 63.8

Hexen-3 (cis) 1.0

Hexene-3 (trans) 5.9

2-methylpentene-1 1.0 4-methylpentene-2 (trans) 0.2

other hexes 0.1

(C) This shows the second stage dimerization. 600 g one Mixture of a normal witch fraction, which is produced in a similar manner

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as prepared under (B) above, and aluminum trihexyl were heated in the weight ratio of 5: 1 in a 1 liter shaking autoclave at the autogenous pressure for 18 hours. A conversion into (^ olefins of 45 »2 i» was achieved.

cLb) Olefin Feed product trans) track 2.3 Heien-1 Gew # ice cream) 26.7 10.8 Witches-2 tear) 62.0 24.8 Witches-2 other witches 0.9 2.8 Witches-3 Dodecenes 7.7 10.3 Witches-3 2.7 3.8 42.5

The product was fractionally distilled to recover the hexenes as a top fraction and then distilled in vacuo, to win the dodecenes. A sample of this dodecene fraction was ijaydrated and the paraffin fraction obtained contained:

n-Dodeeen $ 5

5-methylundecane $ 75>

4-methyldecane 15 # other C ₁ o carbon dioxide

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This distribution of the products in the hydrogenated C. ^ fraction is a sign that the C ^ olefin fraction from which it originates, a highly degradable alkylbenzenesulfonate detergent by. Organisms is.

The Cj2 fraction obtained from the second stage dimerization originated, was condensed at 15 ° C in the usual way with Benaol, using anhydrous hydrogen fluoride as catalyst and the molar ratio of benzene to dodecene fraction was 20: 1. The anhydrous hydrogen fluoride is separated off, remaining traces are removed with aqueous KOH and that

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organic product fractionated to. recover unreacted benzene. The remainder was further fractionated to recover 3 »2 parts of a light alkylate, 123.5 parts of a lowering agent alkylate boiling in the range of 260 to 301 ° C, and 18 parts of a heavy alkylate. The parts are expressed as parts per 100 parts of the C ₁₉ fraction fed.

The cleaning agent alkoxide was sulfonated in the usual way and the sodium salts of the sulfonated alkylate manufactured.

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Claims (12)

Claims 1. A method aur producing a Reinigungsmittelalkylats, characterized in that propylene in the presence of a CATALYSTS, consisting essentially of cobalt on a support of activated carbon, is dimerized to form a to form product which contains a substantial proportion of n-hexenes that a fraction is separated from the product which consists essentially of n-hexenes, this hexene fraction is dimerized in the presence of a catalyst in a second dimerization stage and a fraction of the second dimerization product in the carbon number range C ₁ ,,. up to C ₁ , - with an aromatic carbon IU ΊΟ condensed hydrogen in the presence of an alkylation catalyst will. 2. The method according to claim 1, characterized in that the catalyst for the dimerization of propylene 1-30% by weight Cobalt contains * - 3. The method according to claim 2, characterized in that the catalyst for the dimerization of propylene contains 10-20% by weight of cobalt. 4 ·· Method according to any of the preceding claims, characterized in characterized in that propylene is dimerized at a temperature in the range 2u-200 ° C. 5. The method according to claim 4, characterized in that the. Temperature range is 30-50 ° C. ¹¹ ORIGINAL BATHROOM 809808/0704 6. Verfahr ^ ach each of the preceding claims, characterized characterized in that the fraction consisting essentially of n-hexenes is obtained by fractional distillation of the dimerization product is separated. 7. The method according to any one of the preceding claims, characterized in that the fraction, which consists essentially of n-hexene is, in the presence of a catalyst is dimerized, which is a hydride of aluminum, beryllium, gallium or Indium or derivatives of such hydrides in which one or more of the hydrogen atoms of the hydride are replaced by alkyl or aryl groups are replaced, contains. 8. The method according to claim 7, characterized in that the catalyst contains a trialkyl aluminum. 9. The method according to claim 8, characterized in that the catalyst contains aluminum tri-n-hexyl. 10. The method of any of claims 7-9, characterized in that the second dimerization at a temperature in the range 60-250 ⁰ C is performed. 11. The method according to any one of the preceding claims, characterized characterized in that the fraction is in the carbon number range of C. Q to C-jg from the second dimerization product by fractionated Distillation is separated. 12. The method according to any one of the preceding claims, characterized in that the aromatic hydrocarbon is benzene. 15. Method according to any of the preceding claims, characterized in that that the alkylation catalyst is hydrogen fluoride. 809808/0704 BATH ORIGINAL