DE1126861B - Process for the manufacture of cleaning agents - Google Patents

Description

The invention relates to a method for the production of cleaning agents, which consists of a Surface-active mixture of a salt of a phosphoric acid and a salt of a sulfonated organic Compound or possibly contain this effect and building salts, in which containing the organic compound in a mixture with a phosphoric acid and a free sulfur trioxide Sulphonating agent sulphonated, the resulting acid mixture with an aqueous solution of a Base neutralized and optionally the salt mixture obtained as such or after mixing with Building salts is dried.

In a known embodiment of a method of the above type, the refining waste products from hydrocarbons with alkalis or sulfuric acid or Acid resins with a sulfuric acid halohydrin and fuming sulfuric acid and possibly also one further dehydrating substance, such as metaphosphoric acid, treated mixture, after which the resulting sulfonic acids are absorbed in water and then neutralized. High quality However, surface-active cleaning agents cannot easily be achieved with this method of operation.

According to another known proposal, mixed alkylaryl compounds are used prior to their sulfonation with a phosphorus compound which can be a hypo-, ortho-, meta- or pyro-phosphoric acid can, treated and optionally in admixture with the sulfonatable compound during the sulfonation treatment leave, the sulfonation taking place with 100% sulfuric acid and the phosphoric acid is then separated from the reaction mixture with the spent sulfuric acid before the sulfonation product is neutralized. To achieve a surface-active mixture a salt of a phosphoric acid and an alkylarylsulfonate would be known in this case Process therefore be necessary to convert the phosphoric acid salt into the sulfonation product after deposition of the latter from the previously used phosphoric acid.

According to the invention, an alkylbenzene having an alkyl group containing 9 to 18 carbon atoms or two alkyl groups, one of which has 9 to 13 and the other not more than 2 carbon atoms, is mixed with a phosphoric acid containing more than 1 atom of phosphorus in the molecule with one of 3 to 75 weight percent sulfur trioxide and 97 to 25 weight percent inert gas sulfonating agent in a process of manufacture
of detergents

Applicant:
Universal Oil Products Company,

organized in 1958,
Des Piaines, 111. (V. St. A.)

Representative: Dr. H.-H. Willrath, patent attorney,
Wiesbaden, Hildastr. 32

Claimed priority:
V. St. v. America April 13, 1953 (No. 348 547)

Howard Ernest Mammen, North Riverside, 111.

(V. St. Α.),
has been named as the inventor

Quantity ratio of about 1.1 to 1.4 moles of free sulfur trioxide per mole of alkylbenzene hydrocarbon sulfonated and immediately thereafter neutralized the resulting reaction mixture.

Free sulfur trioxide, d. H. Sulfur trioxide in anhydrous vapor form, has already proven to be a highly active and powerful sulfonating agent for Various organic compounds have been found and is concentrated sulfuric acid and others Sulphonating agents in the processing of alkylaryl hydrocarbons far superior. Nevertheless, its use is in the free state for sulfonation purposes accompanied by various undesirable side reactions which make its usefulness for the Limit sulphonation unless certain changes are made in the normal course of sulphonation which modify its extraordinary activity. So join the unmodified Use of sulfur trioxide a polysulfonation, furthermore a partial oxidation of the organic loading and formation of condensation by-products with resinous or tarry Properties, with the result that the product is discolored and the yield is reduced will. These side effects of free sulfur trioxide are also used with sulfonation observed from alkyl aromatic hydrocarbons with long chain alkyl group. The presence of

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Polysulfonated alkylaryl compounds continues the cleaning power of the desired monosulfonated Products containing products as a whole. The presence of color bodies is also a condition dark colored product, which is less on the buyer appealing and generally poorer cleaning power due to the inclusion of not has cleaning by-products.

It has now been found that the difficulties

To evaporate sulfur trioxide, which the amount of sulfur trioxide required for the sulfonation mixture supplies and the organic feed completely at least in the monosulfoderivat with one Converts the speed with which the suIfonierungsmittel is fed. Another suitable source of gaseous sulfur trioxide is sulfur trioxide vapor, which is formed by the distillation of oleum. Suitable inert carrier gases are e.g. B.

which the use of sulfur trioxide in its io air, nitrogen, sulfur dioxide and gaseous

Hydrocarbons such as methane, ethane, propane and the butanes.

A suitable mixture of sulfur dioxide and sulfur trioxide consists in the product of a

Mixture is converted, which consists primarily of nitrogen, sulfur trioxide and sulfur dioxide. This mixture usually contains between about 5 and about 15 percent by volume trioxide. Before his The sulfur trioxide vapor is introduced into the sulfonation mixture with the inert carrier gas in diluted in such an amount that the gaseous sulfonating agent 3 to 75%, preferably about 5 to

free state can accompany, decrease or even be eliminated by removing the alkylbenzene hydrocarbon feed diluted with a phosphoric acid. This modifies the extraordinary activity of the free sulfur trioxide, in which a mixture adorns and created a liquid medium in which sulfur dioxide and air are catalytically converted into a the sulfur trioxide is converted into complexes with the polyphosphoric acid and gradually out of the Complex is released again as the sulfonation progresses.

In the sulfonation according to the invention, therefore at the same time the monosulfonation of the alkylbenzenes and the yield and nature of the surface-active Product in terms of color, cleaning power

and freedom from undesired by-products, containing 25-30 percent by volume, sulfur trioxide vapor. That promotes. gas flowing out of the suIfonierungsbehälter

The use of monophosphoric acids as captured and recycled. Ortho and metaphosphoric acids are undesirable as polyphosphoric acids for the present daring In the formation of more basic phosphates, those that come into consideration are those in the case of new salts in the neutralization of the sulfonation 30 neutralization polyphosphates of the neutralizing agent mixture in which the ratio of alkali ion per molecule is proportionally higher than in the polyphosphate salts is. The meta- and orthophosphates are also irritating to the skin because of their greater caustic properties Properties in aqueous solution and also 35 Polyphosphoric acid is generally used for the sake of sulfur In an amount corresponding to their lower effectiveness as a build-up salt for alkylbenzenesulfonates, less desirable in the detergent than the corresponding polyphosphates. If desired, the amount used can be

Polyphosphoric acid can be controlled so that a 40 fung of a free flowing liquid mixture that Sulphonation product obtained, which after the new easily, even at relatively low

supply, e.g. pyrophosphoric acid (H ₄ P ₂ O ₇ ), tripolyphosphoric _{acid (H 5} P ₃ O ₁₀ ), hexametaphosphoric acid (H ₆ P ₆ O ₁₈ ) and the less readily available and less preferred hypophosphorous acid (H ₄ P ₂ O ₆ ).

about 0.05 to 2 parts by weight of alkylbenzene were added. The preferred ratio of polyphosphoric acid to hydrocarbon feed lies for the purpose of sheep

trausation contains the desired amount of polyphosphate salts of the neutralizing agent, in general represents about 10 to about 60 percent by weight of the resulting dry detergent.

The method of the invention has the additional Advantage that no intermediate separation of an acidic phase from the sulfonation mixture is necessary is to remove excess acid from it before neutralization.

The starting alkylbenzene used has a replaceable one Hydrogen atom which is exchanged for a sulfo group during the sulfonation reaction and can contain 9 to 18 carbons in one alkyl

Sulfonation temperatures, can be stirred at which the viscosity of the organic charge tends to increase as the sulfonation proceeds about 0.1 and 0.5 parts by weight per part by weight of alkylbenzene. An additional amount of polyphosphoric acid, which is particularly desirable when considering the combined sulfonation and neutralization process operates continuously to a detergent with about 5 to 75 percent by weight To receive polyphosphate salt as a building component is the amount that ultimately has such a Polyphosphate in the finished product results. Polyphosphoric acid is useful with the

Substance atoms or a long-chain alkyl 55 alkylbenzene mixed before this with the sulfomite 9 to 13 carbon atoms a methyl or nierungsnüttel is brought into contact. Contain ethyl group. In this way, particularly desirable cleaning agents are obtained from the alkylarylsulfonate

A favorable sulfonation of the alkylbenzenes will be in the method according to the invention at temperature type, doors of about 10 to 60 ° C. are obtained. The respectively The sulfonating agent provided is practically 60 and depends on the feed and temperature used anhydrous. The inert carrier gas is neither with the other conditions during the sulfonation Sulfur trioxide still reactive with the organic feed. To form the mixture can Sulfur trioxide in its most common liquid

"Gamma" form is placed in a container at relatively high temperatures The preferred sulfonation temperature is that by which an inert carrier gas will tend to sufficient temperature, preferably at about 10 to about 40 ° C, is passed to a portion

away. For the preferred alkylbenzene feedstocks which become easily viscous at low temperatures and in general for discoloration and decomposition

at about 20 to 40 ° C. Depending on the concentration of the sulfur trioxide in the sulfonating agent

however, the temperature can be varied over a considerable range.

The desired amount of alkylbenzene should be given the aforementioned molar ratio of sulfur trioxide to organic feed from about 1.1 to 1 to about 1.4 to 1 within a time of about 0.5 to about 5 hours. The time factor, however, is determined by the intimacy of the touch and affects the speed of heat dissipation.

produced by modifying the various factors. Dodecylbenzene was used with every attempt Sulfur trioxide as an active sulfonating agent, dispersed in dry air, used as an inert carrier gas. 5 The nature of the diluent and of the sulfonation reaction modifying agents were modified to determine their effects.

Dry air which is freed of moisture by passing it through concentrated sulfuric acid

sulfur trioxide brought to dodecylbenzene was approximately 1.1: 1 to 1.2: 1. The outflowing The gas was practically free of sulfur trioxide.

After completion of the sulfonation mixture with the 20 ° / o sodium hydroxide was neutralized until the resulting aqueous slurry a phenolphthalein indicator red colored (p _H about 8.5). The aqueous mixture was then treated with pentane

Vigorous stirring and rapid and effective heat- io was carried out at constant pressure Reduce discharge from the reaction mixture liquid sulfur trioxide passed from 30 ° C. the namely, easily the required contact time. Gas mixture was then added with an additional

The purifying amount of dry air produced according to the process to the desired proportion medium are less corrosive, irritate the human sulfur trioxide set. The resulting sulfur-skins are less and are generally more stable 15 trioxide-air mixture was then introduced into dodecylbenzene as such detergents, which contain free sulfonic acids with stirring, while it is through external. Suitable neutralizing agents are alkali. Cooling was kept at 30 ° C. The total hydroxide, such as sodium and potassium hydroxide, earth amount of the introduced sulfur trioxide, alkali hydroxides, such as calcium and magnesium, was determined periodically by weighing back the sulfur trioxide hydroxide, ammonia, mono-, di- and trialkyl storage bottle, and the reaction was amine, like methylamine or aniline, dimethylamine interrupted when the molar ratio of one and trimethylamine, alkanolamines such as mono-, di- or triethanolamines and other bases. The practically neutral salt mixture should preferably be soluble in water with concentrations that are suitable for the load
use as cleaning agents are effective.

In the method according to the invention, the polyphosphate of the neutralizing agent is inevitably in introduced the product. The resulting mixture

can then be dried and thus contains the extracted 30 to possibly unsulfonated carbon polyphosphate building salt to be separated off in a mixture with the hydrogen sulfide. The extracted aqueous fonat of the neutralizing agent and at least phase was evaporated on a steam bath and a small amount of sulfate salts of the neutral- grind the dry residue to a powder, As a modifier in the experiment, a small excess salt was used to ensure that the monosulfonation was practically complete with a corresponding amount of sodium A shot of sulfur trioxide has been introduced. used mineral acid was mixed in order to

The neutralization of the sulfonation mixture is based on the weight ratio of the builder salt in the cleaning agent to increase to 60:40 until a weakly alkaline mixture is formed. The effectiveness of the Reinivon Sulfonate and phosphate led. The neutralizing agent was in a standard Launder-O-agent the sulfonation 40 meter is preferably measured according to the usual method. at mixture in as concentrated a form as possible to the experiments with modifiers for the sulfonic acid, In order to react to the evaporation of large amounts of water, this was preceded by dodecylbenzene to avoid from the neutralization product. When added to the introduction of the sulfonating agent. z. B. the alkylarylsulfonic acid with sodium hydroxide The amount of modifier for the mines is neutralized this can be obtained as an aqueous solution of about 2 to about 30 percent by weight from 10 to about 30 weight percent can be added. of dodecylbenzene.

The weakly alkaline mixture of Polyphos- In the following series of experiments a ver

Phate and sulphonate can be used in aqueous form immediately with regard to the effect of firstly no modes, but they are preferably used as a pulverizing agent in sulphonation, secondly, sulfur-dried to facilitate packaging and processing, and thirdly phosphoric acid including sand . Before drying, a polyphosphoric acid and other phosphoric acid can also be added as additional structural salts, preferably a poly reaction modifier in the sulfonation phosphate salt, to be added to the reaction mixture,
aqueous slurry formed by the neutralization, in the first attempt dodecylbenzene was used,

the ratio of building salts to sulfonate to 55 which is catalyzed by the hydrogen fluoride to increase the desired level. Generally alkylation of propylene tetramer and benzene such a mixture contains about 60 to about had been produced. The propylene tetramer was 80 percent by weight of building salt, while the rest - by polymerizing propylene over a milichen 40 to 20% of neutral alkylbenzenesulfonate mixture of kieselguhr and pyrophosphoric acid. One of the preferred compositions was 60 and had a boiling range of 170 consists of a mixture of polyphosphate and up to 225 ° C. 246 g (1 mol) of dodecylbenzene were in

brought a flask with a stirrer motor. The flask was kept in an ice bath at about 30 ° C during the ongoing reaction held. In the constantly stirred-65, cooled to 30 ° C dodecylbenzene was a Mixture of about 10 percent by weight of sulfur trioxide, suspended in dry air, initiated and with sufficient speed to about

Alkylbenzenesulfonate with 60 to 65 percent by weight polyphosphate building salt and 35 to 40 percent by weight Alkylbenzenesulfonate salt.

example

A range of sodium alkyl benzene sulfonate detergents was made according to the following procedure

1.1 to 1.2 mol of sulfur trioxide per mol of dodecylbenzene to be introduced within a period of IV2 hours. Under these conditions, however, was the sulfonation mixture is extremely viscous after 15 minutes, which makes the intimate mixing of the Sulfonating agent interfered with the reaction mixture. With a total implementation time of about 45 minutes the reaction mixture assumed a tarry consistency and a dark color, and so did the color became even darker as the reaction progressed. Ice was added to the mixture, followed by so much 20% Caustic soda solution added until the phenolphthalein indicator turned red. Further addition of ice occurred when the heat of neutralization melted the remaining ice. The very dark brown ig aqueous slurry was extracted three times with a quarter of its volume of pentane. The extracts were united and reserved for subsequent treatment. The aqueous residue turned to dryness Vaporized and lifted on a steam bath. The pentane extract was evaporated to dryness and 43 g of dodecylbenzene obtained from the residue, resulting in incomplete sulfonation (83 Vo) of the Indicated alkylate charge. The dried neutral sulfonation product, which as a residue in the Evaporation of the aqueous neutralized slurry obtained was dark brown and contained 37 g Sodium sulfate. Another addition of 390 g of anhydrous sodium sulfate was made to the dry product given a 60:40 ratio of sodium sulfate to achieve sodium dodecylbenzenesulfonate. Then the cleaning power of the agent was im Standard Launder-O-Meter device tested. It was compared to a standard of sodium laurate (assumed equal to 100) 101.% when used the same Concentrations of the standard sample and detergent in the washing solution. An aqueous one The detergent solution left a slightly sticky residue on the surface of the hands.

The second run was similar, except that 100% sulfuric acid was introduced into the dodecylbenzene charge and subjected to sulfonation with the mixture of sulfur trioxide and air. In this experiment, 246 grams of dodecylbenzene (from the same sample of alkylate as in the previous experiment) was placed in a suIfonation flask along with 25 grams of 100% sulfuric acid. The sulfonating agent (10 weight percent sulfur trioxide vapor in air) was added over IV2 hours until approximately 1.2 moles of sulfur trioxide had been introduced per mole of dodecylbenzene. Although this reaction mixture did not become as viscous in the course of the sulfonation as the reaction mixture of the previous experiment without modifying agents, the mixture tended to take on a dark color towards the end of the sulfonation. The reaction mixture was neutralized with 20% sodium hydroxide to a _pH value of about 8.5, the aqueous slurry was extracted with pentane and the extract then evaporated on a steam bath to dryness. 10 grams of dodecylbenzene was recovered from the pentane extract, indicating approximately 96% sulfonation. The dried slurry contained approximately 62 g of sodium sulfate, which was increased to 500 g to obtain a detergent with a ratio of sodium sulfate to sodium dodecylbenzenesulfonate of 60:40, equal to the detergent tested in the first experiment. The dried sludge was a little lighter than the product of the first attempt and can be described as dark cream. The cleaning power (when tested in a standard Launder-O-Meter) was 108% of the sodium laurate under the same test conditions.

The third attempt was 25 grams of pyrophosphoric acid Brought together with 246 g of dodecylbenzene and at 30 ° C with a mixture of air and Sulfur trioxide with a content of 10 percent by volume sulfur trioxide within 1.5 hours sulfonated, introduced into the reaction flask up to about 1.2 moles of sulfur trioxide per mole of dodecylbenzene was. The product was neutralized with 20% sodium hydroxide solution, the pulp with pentane, such as in the previous experiments, pulled out and the aqueous residue evaporated to dryness. 5 g unsulfonated oil was recovered from the pentane extract. The dried aqueous mass contained 37 g sodium pyrophosphate and 28 g sodium sulfate. An equivalent amount of anhydrous sodium sulfate was added to determine the amount of building salt (combined sodium sulfate and sodium pyrophosphate) to increase to 60 percent by weight. The dried residue was light cream in color. The detergency was 125% of the standard mixture containing sodium laurate.

In the fourth experiment, 246 g of dodecylbenzene (1 mol) were introduced into the sulfonation vessel with 75 g of tripolyphosphoric acid and the mixture was again sulfonated for IV2 hours with a mixture of 10% sulfur trioxide in air until 1.2 mol of sulfur trioxide per mole of dodecylbenzene had reacted. The mixture was less viscous than any previous attempt. The sulfonating agent easily mixed with the reaction mixture when the latter was stirred. The sulfonation product was neutralized with aqueous sodium hydroxide to a _pH value of 8.5, extracted with pentane and evaporated the aqueous solution on a steam bath to dryness. The recovery of the unsulfonated oil from the extract provided only 0.5 g of unsulfonated oil, which is more than 99% of the theoretical sulfonation. The dry residue was a light cream color, lighter than the product of the previous experiment, in which 25 g of pyrophosphoric acid was used per mole of dodecylbenzene alkoxide, and contained 107 g of tripolyphosphate together with about 28 g of sodium sulfate. The amount of building salt (sodium tripolyphosphate and sodium sulfate taken together) in the mixture was increased to 60% by adding 390 g of sodium sulfate. When tested under the conditions of the previous tests, the cleaning agent showed a cleaning power of 135% of the sodium laurate standard.

Claims (4)

PATENT CLAIMS: 1. Process for the production of detergents, which consist of the surface-active Consist of a mixture of a phosphate and a sulfonate of an organic compound or optionally contain this mixture and structural salts, by sulfonating a mixture of the organic compound and a phosphoric acid with a sulfonating agent containing free sulfur trioxide, neutralization of the lenden acid mixture with the aqueous solution of a base and optionally drying the salt mixture obtained as such or after mixing with building salts, characterized in that one alkylbenzene with an alkyl group containing 9 to 18 carbon atoms or two alkyl groups, one of which is 9 to 13 and the other has no more than 2 carbon atoms, mixed with a phosphoric acid containing more than 1 atom of phosphorus in the molecule with a sulfonating agent consisting of 3 to 75 percent by weight of sulfur trioxide and 97 to 25 percent by weight of inert gas in a proportion of about 1.1 to 1, 4 moles of free sulfur trioxide per mole of alkylbenzene sulfonated and immediately afterwards the resulting reaction mixture is neutralized. 2. The method according to claim 1, characterized in that the alkylbenzene hydrocarbon in a mixture with pyro, tripoly or Hexametaphosphoric acid with one of 5 to 30 parts by volume of sulfur trioxide vapor and 95 to Sulfonating agent consisting of 70 parts by volume of inert gas sulfonated. 3. The method according to claim 1 or 2, characterized in that the mixture of the alkylbenzene hydrocarbon and the polyphosphoric acid with the gaseous sulfonating agent at a temperature of from about 10 to about 60 ° C sulfonated. 4. Process according to Claims 1 to 3, characterized in that there is a mixture from about 0.05 to about 2 parts by weight of polyphosphoric acid per part by weight of alkylbenzene hydrocarbon sulfonated. Considered publications:
German Patent No. 539 551;
French Patent No. 640 617;
U.S. Patent No. 2,314,255. © 209 558/450 3.