JPS60168793A - Production of basic sulfurized alkaline earth metal phenate detergent - Google Patents

Abstract

PURPOSE:To obtain the titled detergent efficiently, by adding an aliph. prim. 5- 7C alcohol to a starting material mixture consisting of a phenol, sulfur, a dihydric alcohol, an alkaline earth metal reagent, etc. and reacting them. CONSTITUTION:A phenol (e.g. nonylphenol), sulfur, a dihydric alcohol (e.g. ethylene glycol) and an alkaline earth metal reagent (e.g. calcium oxide) composed of an alkaline earth metal oxide or hydroxide are mixed together. Further, an aliph. prim. 5-7C alcohol (e.g. 1-pentanol or 1-hexanol) is added thereto. Water is added to the starting material mixture and the mixture is reacted to effect the metal addition to the phenol and sulfurization. The resulting product is treated with carbon dioxide to obtain the desired basic sulfurized alkaline earth metal phenate detergent.

Description

DETAILED DESCRIPTION OF THE INVENTION ``Futsutsu'' is a basic or overbased sulfurized alkaline earth metal maple phenate type detergent (hereinafter referred to as basic sulfide alkali metal phenate type detergent) which is useful as a detergent for pure oil or fuel oil or as an alkaline detergent. This invention relates to an industrially advantageous method for producing earth metal phenate type detergents. Generally, basic phenate type detergents are used in lubricating oils for internal combustion engines.
It completely neutralizes or disperses acid oils such as oxyacids and sulfuric acid, as well as sludge, lacquer, and carbon, and is highly effective in preventing accidental wear, ring group clogging, and piston ring sticking.

Phenols, sulfur, dihydric alcohols and alkaline earth gold oxides and/or hydroxides are referred to as alkaline earth gold JiJ1 reagents. Many attempts have been made for a long time to produce such basic sulfurized alkaline earth metal phenate detergents by a one-step reaction of sulfurization and gold addition using sulfuric acid as a raw material. For example, U.S. Patent No. 8 (L3
In No. 6971, phenols, sulfur, dihydric alcohols, and alkaline earth metal reagents were reacted without any solvent to perform sulfidation-metal addition, and the product was then treated with carbon dioxide in clean oil to make it basic. Manufactures sulfurized alkaline earth metal phenate type detergents. However, in this method, the organic alkaline earth metal compound formed during the reaction and the intermediate product after the sulfurization-golden addition solidified, becoming a viscous substance, and precipitated as a precipitate. The problem is that the process may not proceed normally, making it difficult to perform tasks such as stirring, transferring, and filtering. Additionally, lubricating oil base oils such as 150 neutral oil, which are generally used as solvents when cleaning phenate-type detergents, have a weak ability to dissolve the intermediate products mentioned above, and are not expected to be sufficiently effective as solvents. I can't.

In order to solve the problems mentioned above, such as the fact that the reaction does not proceed normally when producing basic sulfurized alkaline earth metal 47 eneate type detergents, Japanese Patent No. 588078 was developed.
No. 588079, No. 618542 and No. 61
No. 8548 describes the use of a higher alcohol having 9 or more carbon atoms as a solvent during the reaction, and JP-A No. 54141829 discloses using an excess of phenols as raw materials as a solvent. One of the reasons why we limit our use to higher alcohols with a large number of carbon atoms is that it is necessary to use an excessive amount of dihydric alcohol in the sulfurization-metal addition step in order to almost completely react the alkaline earth metal reagent. However, in order to smoothly carry out the carbonation reaction in the next carbon dioxide treatment process without precipitating solids and to produce a final product that is stable and has good engine performance, it is necessary to carry out the carbonation reaction before the carbon dioxide treatment process. This is because the water produced by the reaction and the excess dihydric alcohol must be distilled off while the higher alcohol in the system remains.

Therefore, it was necessary to select a solvent with a high boiling point for the dihydric alcohol. However, it is necessary to use higher alcohol-soluble IM in an amount of about 0.5 to 9 times or more of the phenol used. Even if the phenol f is used in excess, the amount used is approximately 1.5 (; f or more, preferably about 2.
5 to 6 times the amount is required. If such an excess of higher alcohol or phenol-based solvent is used, the productivity of the reactor vessel M will decrease, and a large amount of utility will be required for heating during the reaction and recovery by distillation after the reaction. (2) Recovery by distillation is industrially disadvantageous because it must be carried out under rather harsh conditions of high temperature and high degree of vacuum.

In addition, the first non-explosion party went ahead (Special Application No. 93, 1987-3).
Phenol power 1, dihydric alcohol, alkaline earth metal reagent - or a mixture of these with sulfur reacted to make phenolic metals! 1' or metal addition and 0
In the reaction that simultaneously degrades the 15-hydrogen compound, adding an appropriate amount of water to the reaction system significantly accelerates the reaction of dilution, metal addition, or sulfide-metal addition.
Basicity (sulfurization) that can significantly increase the conversion rate of alkaline earth gold reagents to products (referred to as !'J product conversion rate) per reaction without the need for excess dihydric alcohol. We have discovered a method for producing alkaline earth gold haphenate type detergents. However, even in this case, it is preferable to use 1j of phenol M1 or a higher alcohol solvent, and the above-mentioned disadvantages ① to ① are alleviated, but they remain.

The present inventors 6(",-1) As mentioned above, the reaction instep is formed by 41 plants of various shapes. As a result of our extensive research into methods that can significantly reduce or significantly reduce the unfavorable effects of glazes that occur when phenols or higher alcohols are used in excess, we have developed a reaction system that does not generate any substances. The purpose of this invention was to find out all the ways in which the objective T- can be achieved by adding water to the reaction system and carrying out the reaction by adding an aliphatic primary alcohol having 5 or 7 carbon atoms to the reaction system. JJ: It is completed.

That is, the gist of the present invention is that phenols, 21i111
A starting material mixture of fluoric acid and an alkaline earth metal reagent is reacted with water to effect metallization and sulfidation of the phenols, and the product is subsequently treated with carbon dioxide back-accumulation. This method for producing a basic sulfurized alkaline earth gold Ak phenate pear detergent is characterized in that an aliphatic primary alcohol having 5 to 7 carbon atoms is added to the starting material mixture and all of the above steps p are carried out. Regardless of the method for producing the basic sulfurized sulfuric earth metal phase detergent2).

One preferred embodiment of the method of the present invention (H is the above-mentioned sulfurized -
Carbonation in the metal addition step and carbon dioxide treatment step V: The reaction is carried out in the presence of an aliphatic primary alcohol of 5 to 7 ml.

A preferred embodiment of the oil in the invention method is the addition of an aliphatic primary alcohol having 5 to 7 carbon atoms and an alkaline earth metal reagent for feed in the sulfidation-metal addition step described in MJ. The reaction is carried out by adding 0.1 to 10 moles, preferably about 0.5 to 4 moles, to the reaction system. Another preferred embodiment is to carry out the reaction in the sulfurization-metal addition step in such a way that the mixing ratio of dihydric alcohol to alkaline earth gold M reagent in the raw materials is within a range of about lθ mol/gram formula amount. .

In this specification, regarding the use of sodium chloride alone and compounds, sulfur 1
The gram formula b↓ shall be expressed as a mouse converted to S regardless of K in the chemical formula, and inorganic compounds shall be expressed in terms of the Crumb formula weight or gram weight. Regarding chemical equivalents, 111 moles of -valent phenol is 1 gram equivalent.

The reaction raw materials used in the present invention will be described.

Misfire 210 Amount of phenol used 1 has 4 to 8 carbon atoms
Hydrocarbon side chains having 6, preferably 8 to 82 carbon atoms, such as argyl groups, alkenyl groups, arostraight groups, etc. I-Metal phenols can be mixed with gold. Specifically, butyl, amyl, octyl, nonyl, dodecyl, cetyl,
Phenols containing ethylhexyl, doriacontyl hydrocarbon groups, or groups governed by petroleum hydrocarbons such as liquid paraffin, wax, and olefin agglomerates (polyethylene, polypropylene, hollybutene, etc.) alone;
Or used as a mixture of these. normal 18
It is desirable to have a liquid state at 0°C, preferably 120°C.

As the alkaline earth metal reagent, oxides or hydroxides of alkaline earth gold Aj4, such as calcium, barium, strontium, magnesium, etc., are used.

The amount of phenols used as alkaline earth metal reagents can vary widely; for example, the amount of phenol used,
ki is alkaline earth gold J'J4 reagent 1 gram formula -1, equivalent, about 0.1 to 6 moles, preferably about 0.4 to 2.0 moles.

If the amount of phenol is too small compared to the alkaline earth metal reagent, Nagato's unreacted alkaline earth metal reagent will be generated in one reaction, and if too much is used up, the ) The advantages of the present invention are reduced.

Next, as the dihydric alcohol, one having a relatively low boiling point, low viscosity, and high reactivity is used. The dihydric alcohol preferably has 2 to 6 carbon atoms, and ethylene glycol and propylene glycol are preferable. The amount of dihydric alcohol used is about 0.3 to 1,0 mol per gram of alkaline earth gold L4 reagent, particularly preferably about 0.4 to 0.
．． It is 8 moles. Dihydric alcohol is pheno-A13R:
The reaction with the alkaline earth metal reagent helps in converting it into an oil-soluble substance, stabilizes it, and partially incorporates it into the V-crystalline phenate to produce a large quantity of phenate. ：It is something that will be established.
If the amount of dihydric alcohol used is too small, the product conversion rate of the alkaline soil reagent will decrease due to the reaction mixture, and 2i11. ++ If too much alcohol is used, the amount of dihydric alcohol in the product will be large and it will have an unfavorable effect on engine performance, so don't worry! It is not necessary to completely distill off the excess portion after the vulcanization and sulfurization reactions, which is not efficient. However, in the method of the present invention, the amount of dihydric alcohol used is generally smaller than in the conventional method.
This simplifies the process of evaporating the dihydric alcohol. When a large amount of dihydric alcohol is used in the method of the present invention, C3 to C1 are distilled together with the dihydric alcohol.
If the amount of the aliphatic primary alcohol is large, it may be necessary to add a ladle of C6 to C7 aliphatic primary alcohol before the carbonation reaction, which is not efficient.

Sulfur (elementary sulfur) can be used in a wide range of amounts in the present invention, from very small amounts to large amounts.

Usual Use - A formula weight of about 4.0 grams or less, particularly about 0.05 to 3.0 grams, per 1 gram formula weight of a 1μ alkaline earth metal reagent is preferred. If the amount of sulfur used is too large, it becomes difficult to obtain a basic 7-enate type shield detergent.

In the metal addition reaction process of alkaline earth gold plate reagents to phenols, not only aqueous water added to the reaction system, distilled water, but also canned water, industrial water, water produced in the metal addition reaction, etc. can be used, and there are particular restrictions on their quality. It can be used in any state of water, including cold water, hot water, and steam. Water can be added to the reactor either alone or in part or in its entirety as a mixture of gold furkylphenol, dihydric flucol, C3 to Ct Ili', and other raw materials such as aliphatic primary alcohols and higher alcohols. It's okay. There are no restrictions on the timing of adding water to the reactor, and all reaction materials are mixed after water = 1
Although it may be added within 1 hour or later, it is preferably added within about 1 hour after mixing all the reaction materials. The amount of water added to the reaction system is approximately 0.01 per gram of the alkaline earth metal reagent used.
~1O Durham formula weight preferably 0.1 to 240 grams. When a metal addition reaction is carried out by adding water into the reaction system from the outside, the reaction progresses by tJ1 ft1l', and the reaction raw material is In particular, alkaline earth metals increase drug reaction rates and product conversion.

In the present invention, an aliphatic primary alcohol having 5 to 7 carbon atoms is used as a solvent. Examples of this primary alcohol include l-pentanol, 1-hexanol, l-heptatool, 8-methyl-1-butanol (isoamyl alcohol), 4-methyl-1-pentanol (inhexyl alcohol), -Methyl-1-hexanol (inhebutyl alcohol), or a mixture of two or more thereof. This C6-C7 aliphatic primary alcohol may be straight-chain or branched, but straight-chain is preferred. By using this C1-C7 aliphatic primary alcohol, the reaction proceeds smoothly and produces a basic 010 alkaline earth metal phenate type detergent with good properties. It should be noted that this kind of effect is C6~C7
It is specific only to primary alcohols; secondary alcohols, secondary alcohols, aromatic hydrocarbons, ethers, n-butanol, etc. undergo gelation during metal addition, sulfurization, or carbonation reactions. This may cause abnormal reactions such as 2 decomposition.

From this meaning, C6~C? ＄Primary alcohol is not just a solvent, but is involved in a single reaction (/C), and a part of it may be incorporated into the product as VC, but the details are unknown.C, ~ C. After completion of the reaction or after removing a small amount of insoluble substances present by filtration, the primary alcohol is distilled together with unreacted dihydric alcohol, unreacted phenols, etc.J15j71. , can be used cyclically.

When using high-grade a7L gold with carbon number of 8 or more, the above ■~
As described in (2), there are problems such as decreased productivity, increased utility costs, and the hassle of using the old 1 revenue.

The above C-glue C-cho aliphatic primary alcohol can also be used together with other co-solvents such as tj-runpo, oil base oil, and hydrocarbon solvents. These solvents may be used alone or with phenol and/or
Alternatively, the alkaline earth metal can be mixed with dihydric alcohol and/or water and supplied to the reactor. Fri) After the V + second addition and the % fE conversion reaction O.h7, the added water and the water produced by the reaction are slightly removed from the system, but at this time, a part of the solvent is azeotropically distilled with the water. Sometimes things get weird. The distilled water-bath medium mixture can be recovered by distillation and used in 6L, and some of the water-bath medium mixture can be used as is for the next reaction. It can be used as raw stone and can be recycled with virtually no loss. The remaining portion after water distillation is a transparent or translucent liquid due to the presence of the solvent.
It is possible to subject the product to the next carbonation step. After the carbonation reaction is completed, the solvent is recovered by distillation from the reaction product mixture together with unreacted phenols and unreacted dihydric alcohol, but the mixture can be used as a raw material for the next reaction. Appropriate use of the C3-C1 aliphatic M primary alcohol solvent 41 is based on the amount of co-solvents such as lubricating oil base oil, excess phenols (f(:X part) other than the part that reacts and converts into products), etc. It depends on the
In the sulfidation-metal addition step, the amount of alkaline earth metal reagent used is preferably about 0.1 to 10 mol, particularly about 0.2 to 10 mol, preferably about 0.5 to 4 mol, per gram formula ti of the alkaline earth metal reagent used; In the carbon dioxide treatment step, 1 gram of the alkaline earth metal reagent raw material used was approximately 0.0%. (J5 to 10 mol, preferably about 0.2 to 4 mol.C6 to C2
If the amount of aliphatic primary alcohol used is too small, sulfurization will occur.
The viscosity of the intermediate product after the metal addition reaction becomes so high that it becomes difficult to handle it, the product becomes assimilated (gelled), or an abnormal reaction occurs. On the other hand, if the amount used is too large, a large amount of energy tM will be consumed in the heating during the reaction and in the solvent recovery process, and the productivity per unit reaction bM equivalent will be low.

The main manufacturing process and operating conditions of the basic sulfurized alkaline earth metal phenate type detergent according to the present invention V are as follows.

(a) Sulfurization-metal addition process Phenols, sulfuric acid, alkaline earth gold}7Δ test system, C3 to C7 aliphatic primary alcohol is added to the dihydric alcohol, and water is added before or during the reaction. ;,, and perform the reaction. The reaction temperature is approximately (50-20 (lu,
The reaction is preferably carried out at a temperature of approximately 90 to 190°C. The reaction can be carried out under normal pressure, but may also be carried out under an increased pressure of about θ to 10 atmG in order to maintain water in the system. In addition, in order to make the reaction proceed smoothly, the order in which each raw material is charged into the reaction vessel is that the alkaline earth metal reagent is added after the phenol or solvent, and the dihydric alcohol and water are added last after the alkaline earth metal reagent. is preferable.

During this step, a sulfurization reaction also occurs simultaneously with the metal addition reaction of phenols. It is desirable to remove hydrogen sulfide generated during the reaction from the reaction system.

This reaction is usually almost completed within a range of about 1 to 9 hours.

It is preferred that the added water and the water produced during the reaction be substantially completely distilled off after the reaction L6. At this time, a part of the solvent may be azeotropically distilled with water and distilled out of the system, but the distilled water-solvent mixture can be recovered by phase separation, etc. as described above, and then the water and water can be distilled off. - Can be reused as a raw material next time as a solvent mixture. Alternatively, the distilled water-solvent mixture may be partially separated by phase separation or the like, and the water-rich layer may be removed from the system while the solvent-rich layer is returned to the system. If water remains in the final product, the stability of the product will be poor, and when the product is treated with carbon dioxide after this reaction, if a large amount of water remains in the system, the filtration performance will decrease and the desired basic alkali 1) Earth metal and phenate type detergents may become separated. In the present invention, since only a small amount of dihydric alcohol remains in the reaction product of this reaction, it is not necessary to substantially distill off the dihydric alcohol, and the overall distillation time can be shortened.

(b) Carbon dioxide treatment process In order to further increase the stability and oil solubility of the product, the liquid distillation residue after completing the sulfurization-metal addition reaction process is placed in an autoclave, and the reaction temperature is preferably about 50-280°C. is about 80 to 200°C, reaction pressure is about 0 to 50 at
The reaction is carried out with carbon dioxide under conditions of mG, preferably about θ to 20 atrrIG. If necessary, this product may be further heated under an atmosphere of carbon dioxide, preferably under pressure (θ~50 atm).
G, preferably 0-20atrrIG), about 100-2
Several minutes to more than ten hours at 80°C, preferably about 0.5
~Hold for IO time. In the carbon dioxide treatment step, carbon dioxide is reacted and introduced into the side chains of phenols and the phenolic aromatic nucleus. When the reaction product was analyzed after hydrolysis, a salicylate skeleton was also detected in addition to the enate skeleton. The carbon dioxide treatment further improves the performance of the product as a lubricating oil additive and fuel oil additive (in particular, the cleanliness and stability of engine oil when added to engine oil).

In addition, if you are an expert, you can add an alkaline earth metal reagent and a dihydric alcohol to the reaction product after carbon dioxide treatment, perform the metal addition reaction as described above, and then perform a series of operations such as carbon dioxide treatment. It is also possible to add more gold stakes by repeating the steps one or more times. From an economic standpoint, it is preferable to recover most of the solvent and unreacted phenols in the reaction product after carbon dioxide treatment by distillation or the like. Furthermore, the recovered solvents can be reused as raw materials while still containing the recovered phenols. In addition, the small amount of dihydric alcohol L dioxide remaining after the metal addition reaction step can be recovered together with unreacted phenols and the like after treatment. Note that if the solvent and unreacted phenols are distilled in the presence of a common diluent (co-solvent) for the product phenate, such as Takana point mineral oil, the distillation residue will be in a liquid form (which can be obtained by Such a diluent can be added as a co-solvent together with the solvent from the beginning of the VC reaction, or it can be added after the carbonation reaction is completed. 6 Before or after collecting the non-bath dissolvable materials and phenols in the waste.
1 minute or centrifugation! The gap can be removed by a movement such as +i1.

Although the exact structure of the reaction product of the method of the present invention is unknown, the oil layer obtained by hydrolyzing the reaction product and extracting it with a solvent such as hydrolyzate/X-san. Since both lytic acid and phenol4 were detected, it is thought that some of the raw material phenols were converted to salicylate by reaction with carbon dioxide. In addition, since the reaction products haphenols and salicylic acid contain 9 or more alkaline earth metals per gram equivalent, the product is a basic alkaline earth metal salicylate or a basic alkaline earth metal salicylate. It is thought to contain cores of sulfurized alkaline earth metal salicylate and basic sulfurized alkaline earth metal phenate. On the other hand, is the reaction product a mixture of molecules containing only salicylate bone cores and molecules containing only phenate bone cores, or is it a compound containing both salicylate bone cores and phenate bone cores in one molecule? The details of the binding mode of the salicylate bone core and the phenate bone core with the alkaline earth metal element, the reacted sulfur, and the reacted dihydric alcohol are unknown;
Furthermore, the bonding mode of carbon dioxide other than that used for conversion into salicylate among the reacted carbon dioxide in the product is unclear, and the reaction product of the present invention is a basic sulfurized alkaline earth metal salicylate or a basic sulfurized alkaline earth metal salicylate. It can also be called a complex of basic alkaline earth gold salicylate and basic sulfurized alkaline earth metal phenate. As mentioned above, although the detailed structure of the reaction product of the present invention is unknown, the basic alkaline earth metal salicylate bone core or the basic sulfurized alkaline earth metal salicylate bone core and the relatively common combination of Since the sulfurized alkaline earth gold maple has a phenate bone core, the reaction product is herein described as a basic sulfurized alkaline earth gold LL phenate shop purifier. However, as mentioned above, this name does not describe the exact chemical name,
Further, the present invention is not in any way bound by the above-mentioned presumption or theory, and the above-mentioned names are used simply for convenience of understanding.

As described above, according to the present invention, by using a small amount of a specific C6-C7 alcohol as a total solvent, the reaction can be carried out smoothly, and the conversion rate of the reaction raw material, especially the alkaline earth metal reagent, can be kept high, and it can be used for lubricating oil and fuel. It is possible to produce a basic sulfurized alkaline earth metal sulfate type detergent that has good performance as a detergent for carbonated oil, and therefore has high productivity per reaction vessel equivalent, and requires less amount of CB-C7 alcohol to be used. Furthermore, since the boiling point is low, less utilities are required for the reaction, and recovery is easy.

The present invention will be explained below with reference to Examples.

Example 1 1.0 mol (2
zo,'at), 0.7 crumb formula % sulfur (255,5f) and 1.0 gram formula weight (58,4+?) of calcium oxide with a purity of 96.0 wt% were added and heated with stirring. To the resulting suspension was added 0.55 moles of ethylene glycol and 0.6 grams of water.
A (io, sr) mixture in a total nitrogen stream at 2.0 atm
G, added at 125°C, this Th 18UC12, Q
The mixture was heated and stirred in atmG for 8 hours to remove the purple sulfide while carrying out all metal separation and sulfurization reactions.

Next, the added water and the produced water were distilled off while gradually reducing the pressure in the reaction system. At this time, in order to completely remove water and gold, distillation was continued until 50 f of 1-hexanol was distilled out (azeotrope composition; water to 1-hexanol heavy oxide ratio was 67
, z vs. 82.8).

The distillation residue obtained was a dark green viscous liquid.

This intermediate product obtained was placed in an autoclave as Q~5a.
tu+G, 80 at temperature 120℃ under pressure of maximum 5 atmG
Carbon dioxide was allowed to absorb for minutes. Next, the carbonation reaction was completed by holding at 155° C. for 2 hours under a pressure of 5 atrnG using tA hydrogen dioxide. Using this reaction product solution as a diluent, 150% neutral oil 242.8 ? The product mixture (Il-filtered to remove traces of insoluble 8'r,
I got the liquid. 2.Pour the P solution into a 20 pear-shaped flask and distill it under reduced pressure to remove the solvent 1-hexanol and unreacted nonylphenol and ethylene glycol. Object 486°8.91
Obtained. The final distillation temperature of the gap was 155°C (1+m+l flat).

The M1 conversion rate of the alkaline earth metal material and the properties of the final basic sulfurized alkaline earth metal phenate type detergent are shown in Table 1.

In the table, the product conversion rate of raw materials refers to the ratio of raw materials incorporated into the final product, and the gold addition equivalence ratio refers to the ratio of alkaline earth metal reagents incorporated into the final product to phenols (excluding free phenols). ) is the gram equivalent ratio of A portion of this final product was subjected to column chroma l-' using silica gel as an adsorbent and 1Cn- to Keelin as a substituent to isolate the active ingredient. The isolated yellow powder active ingredient was added to an excess of I
Analysis of the oil layer obtained by hydrolysis using NH, So, and aqueous solutions by liquid chromatography revealed that 58% of nonylphenol, which constitutes the active ingredient 'lictS, was converted to nonyl salicylate.

Example 2 Basic alkali metal sulfide J
All l'l phenate-type disinfectants were manufactured.

1 distilled in the water expulsion process after the monometal sulfide addition process
-Pentanol was concentrated at 43.1 f (azeotrope composition; weight ratio of water to l-bentanol was 54, 4 to 45.6
). The yield of the final product was 451, 6r, and the conversion rate of nonylphenol to salicylate, Q, was 5.0 mol%.

The product conversion rate of raw materials and the properties of the final product are the same as those of the younger brother.

Practical Example 8 In the same autoclave as used in Example 1, 1.0 mol s of nonylphenol {+iirX<o. 7 grams formula weight, solvent 1-11 Kidunol 1.0 mol (io2.!M
), 150 neutral oil (resistance 5.89CS) as an auxiliary flood medium
(99°C) Pacifin type lubricant oil) 242.8F and oxidizing power 10g formula. i11 was charged, and the heating loss was r1. Seasoned suspension l - ethylene glycol 0
Nitrogen'J (125°C, 2 atmQ in a stream of 0 air was added to a mixture of 55 ml and 00 ml of water at 180°C, 2 atmQ).
Q atmG for 3 hours r:j”la stirring L te Wt
While removing the hydrogen sulfide 'it=k, a gold sulfide 6-addition reaction is carried out and the result is 7.

Next, the pressure of this reaction system +noq- was gradually reduced, and the water in the system was distilled off. In order to completely remove this raw water, l-hequidunol 501 was also distilled off.

The resulting X residue was placed in an autoclave for 0 to 5 at
mG, maximum 5at, under pressure of mG;,'r F ],
Nu dioxide was absorbed at 20° C. for 80 minutes. Then, the mixture was maintained at 75° C. for 2 hours under a pressure of 5 atrr with carbon dioxide to complete the oxidation reaction. The resulting mixture was passed through a furnace 41 to remove a very small amount of undissolved matter. The obtained r liquid was placed in a pear flask using 2 and distilled under reduced pressure to remove the dissolved IA]-hegizanol, most of the unreacted nonylphenol, and all of the unreacted ethylene glycol, and the final product was the distillation residue. 473.8f was obtained. The final distillation temperature at that time was 155°C (1 Hf).

result? Shown in Table 1. In addition, the conversion rate of nonylphenol to salicylate in the final product of the basic sulfurized alkaline earth metal phenate type detergent was 6.8 mol %.

Chapter l Shishi (Note) *Base number is based on JIS K 2500GC.

Comparative Example 1 1-Butanol 4 was used instead of 1-hexanol as a solvent.
．． The same operation as in Example 1 was carried out except that 0 mol (296.5 mol) was used. In order to completely remove water in the step of distilling off water after the sulfide-metallic processing step, 126.89 fI of l-butanol was distilled out. 150 neutral oil 242.3 in the reaction product solution after the carbon dioxide treatment step
During the operation of adding t and recovering the solvent and unreacted nonylphenol, the contents gelled and a normal product could not be obtained.

Comparative Example 2 The same operation as in Example 1 was carried out except that 2.2 mol (220y) of cyclohexanol was used in place of 1-hexanol as the solvent. In the step of distilling off water after the sulfurization-metal addition step, 80f4 of cyclohexanol was distilled off to completely remove water. 150 neutral oil 24.2.8 f f into the reaction product solution after the carbon dioxide treatment step
In addition, during the operation to recover the solvent and unreacted nonylphenol, the contents gelled, making it impossible to obtain a normal product.

Comparative Example 8 The same operation as in Example 1 was carried out except that 2.5 mol (220,4y) of 2-benkenol was used in place of 1-hexanol as the solvent. In order to completely remove water in the step of distilling off water after the sulfurization-metallic processing step, 2-pentanol 5Of'f: was distilled off. During the carbon dioxide treatment process, the contents underwent a decomposition reaction and the target product could not be quenched.

Comparative Example 4 The same operation as in Example 1 was carried out except that 5.2 mol (880.5y) of xylene was used instead of 1-hexanol as the solvent. Product conversion rate of calcium oxide is 40% due to incomplete reaction of sulfidation-metal addition step.
It was low.

Example 4 8-Methyl-1- to l-hexanol as a solvent
A basic sulfurized alkaline earth Kanetsuki phenate type seedling detergent was prepared in exactly the same manner as in Example 1 except that Butanol 22 (103,6y) was used.The results are shown in Table 2.

Moreover, the final product had a settling temperature of 4r53.7F.

Example 5 Total amount of nonylphenol used was 0.5 mol (110,22
) A basic sulfurized alkaline earth metal implanted phenate type detergent was produced in exactly the same manner as in Example 1. The results are shown in Part 2. Moreover, the yield of the final product was 481.8F.

Claims (1)

[Claims] Adding water to a starting material mixture consisting of phenols, sulfur, dihydric alcohols, and alkaline earth metal reagents consisting of alkaline earth metal scrap oxides and/or hydroxides, and reacting the metals of phenols. and sulfurization,
A method for producing a basic sulfurized alkaline earth metal phenate odor detergent comprising subsequently treating the product with carbon dioxide, in which an aliphatic primary alcohol having 5 to 7 carbon atoms is added to the starting material mixture. jR manufacturing method of a salt lfk sulfurized alkaline earth metal phenate type detergent, which is characterized by carrying out the above steps.