JPH07150180A - Method of overbased phenate - Google Patents

Abstract

PURPOSE: To obtain an overbased sulfurized alkaline earth metal alkylphenate by a batch process, by which a throughput rate is increased, by introducing CO₂ simultaneously with a base of an alkaline earth metal to carry out carbonation by a single step.

CONSTITUTION: A mixture essentially composed of an alkylphenol, sulfur, a solvent for promoter, and a base of an alkaline earth metal is brought into contact under reaction conditions in a reactor to form a sulfurized, alkaline earth metal alkylphenate by feeding the base of an alkaline earth metal, the solvent for promoter, and carbon dioxide simultaneously to a reaction zone for reaction under reaction conditions at a molar ratio of carbon dioxide/the alkaline earth metal base of 0.40:1 to 0.95:1 and, at a feed rate which is substantially greater than a reaction rates of carbon dioxide, the alkaline earth metal base and the sulfurized alkaline earth metal alkylphenate, or at a controlled smaller feed rate, thereby overbasing the sulfurized alkaline earth metal alkylphenate. The charge of carbon dioxide is continued until completion of the reaction.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

The present invention generally relates to the reaction of alkaline earth metal bases, sulfur and alkylphenols first in the presence of a mutual solvent to form an intermediate of a sulfurized metal phenate, which is then added to an additional alkali. The present invention relates to a method for producing an overbased sulfurized alkaline earth metal alkylphenate which is overbased by carbon dioxide in the presence of an earth metal base. In particular, the present invention introduces CO ₂ into the reactor at the same time as the introduction of the alkaline earth metal base with a magnetic tape that defines the CO ₂ / alkaline earth metal base,
It relates to a batch method in which the carbon dioxide conversion step is carried out in a single step, whereby the throughput is substantially increased.

Lubricating oils tend to deteriorate under the normal conditions encountered in today's diesel and automotive engines. Sludge, lacquer and resinous material formed,
It adheres to parts of the engine, especially piston rings, grooves and skirts, which can have a detrimental effect on engine efficiency, operation and useful life. Normally,
Additives are incorporated into lubricating oils to reduce the formation of such materials and hold them in suspension, thus keeping parts of the engine clean and operating properly.
Additives that reduce the tendency of lubricating oils to form oxidation products are called antioxidants, but tend to suspend oxidation products and sludge or clean such products from engine parts. The additive is called a detergent or dispersant. It is not unusual for certain additives to have both antioxidant and detergent properties.

It has been discovered that overbased sulfurized alkaline earth metal alkylphenates are particularly useful in lubricating oils for the dual purpose of providing oxidation inhibition and detergency.

The term "overbased" refers to the fact that the phenate material incorporates a large excess of alkaline earth metal base over that required for its neutralization. Typically, the overbased phenate has a TBN of about 100-400.
(Total number of bases). Such high basicity allows the additive to neutralize the harmful acids formed during engine combustion, and carbon dioxide (carbon).
cation) or carbonic acid overbasing (carbonate)
This is accomplished using the well known technique commonly referred to as overbasing). This technique generally involves the formation of an initial alkaline earth metal sulfurized phenate intermediate with relatively low levels of metal base. This intermediate is then treated with an excess of additional alkaline earth metal. In a less well understood reaction, the sulfurized metal phenate intermediate is reacted with an excess of metal base in a suitable solvent, usually glycol, by bubbling gaseous carbon dioxide into the reaction components. Treatment of CO ₂ or carbon dioxide forms a fine colloidal dispersion which essentially “dissolves” the excess metal base.

The production of overbased sulfurized alkaline earth metal alkylphenates by a batch or continuous process comprises:
Well known in the art. There are significant advantages and disadvantages associated with both types of treatment.

For example, the batch process, as expected, has the major drawback that much less product can be produced over a given period of time than when using a continuous process. Nevertheless, a very significant advantage of the batch method is that the bottom of carbon dioxide can be controlled very closely and reliably. This is important. This is because the excessive carbonation or lack of carbonation of the overbased phenate is a serious problem. Overcarbonated products generally exhibit poor water durability in lubricating oil formulations and become cloudy due to the destruction of the colloidal dispersions described above. Products lacking carbon dioxide increase viscosity, have poor filterability, and are difficult to remove glycols. The batch method avoids these problems and is the method of choice, especially when water-resistant phenates are an important objective.

Continuous processing has the advantage of maximizing the throughput of production. However, in a continuous process, the first reactor is typically used to effect the formation of the initial sulfurized metal phenate intermediate, while the second reactor or series of consecutive reactors is carbonized. To use for. A well-known phenomenon associated with continuous processes is that of residence time distribution. This phenomenon is particularly harmful in the carbon dioxide conversion process of the continuous phenate method. This is because it forms both overcarbonated and undercarbonated phenates. For this reason, overbased phenates produced by the continuous process generally yield significantly poorer water durability than phenates produced by the batch process. The phenomenon of residence time distribution can be minimized by increasing the number of reactors used for the carbon dioxide process to mimic a plug flow reactor, but with substantial capital outlay. .

Ideally, it would be desirable to combine the throughput of production in a continuous process and the control of carbon dioxide provided by a batch process to obtain a phenate with very good water endurance properties.

A number of patents on the production of overbased sulfurized alkaline earth metal alkylphenates are produced. Belgian Patent No. 876,119 is most relevant,
Disclosed is a method of making a sulfurized overbased alkaline earth metal alkylphenate, comprising:
The group metal base, the alkylphenol and the mutual solvent are contacted in a heat exchanger for a time sufficient to form the metal phenate, and then the phenate is passed into the reaction zone without substantial cooling, wherein said metal Formation of the sulfurized metal phenate intermediate is accomplished by contacting the phenate with sulfur under reaction conditions to form the sulfurized metal phenate intermediate. This intermediate can then be carbonated with CO ₂ . This patent describes a "quasi-batch" process, in which the reaction components are added to the reactor while the reaction is taking place, but this patent is concerned with the unique carbon dioxide adoption employed in the present invention. Does not teach or suggest means.

A general object of the present invention is to provide a batch process which produces overbased metal phenates with improved throughput of production while avoiding the disadvantages associated with continuous processes. Other purposes will be apparent to those skilled in the art thereafter.

The present invention comprises the steps: (a) contacting a mixture consisting essentially of an alkylphenol, sulfur, a solvent of a promoter and a base of an alkaline earth metal in a reactor under reaction conditions to form an alkali sulfide. Forming an earth metal alkylphenate, and then (b) under reaction conditions (i) an alkaline earth metal base, (ii) a promoter solvent and (iii)
Carbon dioxide at a carbon dioxide / alkaline earth metal base molar ratio of about 0.40: 1 to about 0.95: 1 and carbon dioxide, an alkaline earth metal base and a sulfurized alkaline earth metal alkylphenate. The sulfurized alkaline earth metal alkylphenate formed in (a) above is simultaneously fed to and reacted in a reaction zone at a controlled rate that is substantially no greater than or less than the rate at which it reacts. Overbasing, and (c)
When the supply of the alkaline earth metal compound and the solvent for the promoter to the reaction zone is completed, the supply of the carbon dioxide is continued until the reaction is completed, and the overbased sulfurized alkaline earth metal alkylphenate is produced. Is the way to do it.

[0012] In a related embodiment, the invention further comprises a step: (a) a mixture consisting essentially of an alkaline earth metal base and an alkylphenol in a molar ratio of about 0.1: 1 to about 1.0: 1. Is fed through a preheating means into the reactor where the mixture is about 137.8-193.3.
Entry into a reactor preheated to a temperature of about 280 to 380 ° C; in the reactor at the same time about 0.1 to 1.0 mole of promoter solvent per mole of alkylphenol. And then (b) reactor about 137.8.
˜193.3 ° C. (about 280 to 380 ° F.), while maintaining a temperature of about 1.0 per mole of alkylphenol in the reactor over a time period of about 20 to 180 minutes.
˜about 2.0 moles of sulfur are added, and (c) when the sulfur addition is complete, the reactor is allowed to react at the reaction temperature for a time sufficient to form a sulfurized alkaline earth metal alkylphenate. Interacting contents, (d) about 13
At a temperature of about 280 to about 380 ° F (7.8 to about 193.3 ° C), is the reaction components present in the reactor substantially greater than the rate at which they react to form an overbased phenate? Or (i) at a controlled feed rate which is not small, (i) from about 0.5 to about 2.0 moles of alkaline earth metal base per mole of alkylphenol, (i)
i) about 0.5 to about 2.0 moles of promoter solvent per mole of alkylphenol and (iii) about 0.40 to about 0.95 moles of carbon dioxide gas per mole of alkaline earth metal base. Are simultaneously fed into and reacted in the reactor to convert the sulfurized alkaline earth metal alkyl phenate to an overbased phenate, and (e) an alkaline earth metal base and promoter. When the supply of the solvent to the reactor is completed, the supply of the carbon dioxide is continued until the completion of the carbonation reaction, and the method for producing an overbased sulfurized alkaline earth metal alkylphenate.

Although the present invention can be considered a batch method,
The carbonation process used in this process significantly reduces the reaction cycle time so that this process can reach or equal the throughput of continuous process production. Contrary to feeding the alkylphenol and metal base at ambient temperature and waiting for the reactor to heat to the desired reaction temperature, the sulfurization step utilizes preheating means, as required in the relevant embodiment above. Further introduction of alkylphenols and metal bases into the reactor at the reaction temperature can achieve further reductions in the reaction cycle time. The overbased phenates produced using the method of the present invention exhibit the very good water endurance properties normally associated with batch processes, while the process has a typical reaction cycle time of 9-10 hours for batch reactions. Can be reduced as much as 4 to 5 hours.

In general, the process of the present invention can be carried out in two stages in a single commercial size stirred tank reactor. In the first step, the sulfurized alkaline earth metal alkylphenate intermediate is prepared by contacting the appropriate alkylphenate, alkaline earth metal base and sulfur under reaction conditions in the presence of a promoter or mutual solvent. Form. In the second stage of this process (carbonation), the sulfurized metal phenate intermediate is treated with CO ₂ gas in the presence of additional amounts of alkaline earth metal base and promoter solvent. By making certain modifications to one or both of these stages, the present invention dramatically reduces the reaction cycle time required to produce a finished batch of overbased phenate product. Each of the two stages will now be described in more detail.

Formation of Sulfided Metal Phenate Intermediates At the front end of the process of the present invention, an alkylphenol, an alkaline earth metal base and sulfur are reacted in the presence of a promoter solvent to form a sulfurized metal phenate.

Alkylphenols useful in the present invention have the formula R (C ₆ H ₄ ) OH, where 8 to 40 R,
Preferably a linear or branched alkyl group having 10 to 30 carbon atoms and a moiety (C ₆ H ₄ ).
Is a benzene ring. Examples of suitable alkyl groups are octyl, decyl, dodecyl, tetradecyl, hexadecyl and the like.

The alkaline earth metal base is calcium,
Barium, magnesium and strontium.
Calcium and magnesium are preferred. The most commonly used bases are the oxides and hydroxides of the above metals,
For example, calcium oxide, calcium hydroxide, barium oxide, magnesium oxide and the like. Calcium hydroxide, commonly referred to as hydrated lime, is the most commonly used in the production of sulfurized calcium phenates and is of excellent quality (relatively carbonate free) which has not deteriorated during storage. It is preferable to use hydrated lime of.

The promoter solvent, also sometimes referred to as a mutual solvent, is any stable organic liquid that has appreciable solubility in both alkaline earth metal bases, alkylphenols and sulfurized metal phenate intermediates. Can be Although a wide variety of molten sulfur is known in the art, many such suitable sintered bodies are glycols and glycol monoethers such as ethylene glycol, 1,4-butanediol, derivatives of ethylene glycol. , For example, monomethyl ether, monoethyl ether and the like. Vic-glycol is preferred, and ethylene glycol is most preferred and represents the neutralization reaction to the extent that it serves to activate the neutralization reaction, but the exact properties describing its function are not known.

The sulfur used in this reaction is elemental sulfur. In the present invention, it has been discovered that it is desirable to use molten sulfur.

In the present invention, it is more desirable, but not required, to use low base alkylbenzene sulfonates as promoters in the formation of sulfurized phenates. Sulfonates suitable for use are, for example, those obtained by sulfonation of alkyl-benzenes derived from polymers of olefins or C ₂ -C ₄ olefins with a chain length of C ₁₅ -C ₈₀ , preferably with a molecular weight below 400. Sulfonic acids and alkaline earth metals, such as calcium,
Salts such as barium and magnesium. In the next example of this description, a low base calcium sulfonate made from polypropane with a chain length of about C-60 was included in the sulfurization reaction.

In addition to the above reaction components, the formation of the sulfurized metal phenate is preferably carried out in the presence of a lubricating oil reactive diluent. The lubricating oil includes any lubricating oil used in the final lubricating oil formulation containing the phenates produced according to the present invention, including naphthenic bases, paraffin bases and mixed base mineral oils, 5W, 10W. Or it could be event 40W oil. 5W oil is generally most suitable as the reaction diluent.

The range of reaction stoichiometry for the above reaction components is as follows:

[0023]

Table 1 Range Preferred range Sulfur, mol / mol DDP * 1.0-2.0 1.3-1.6 Ca (OH) ₂ , mol / mol DDP 0.1-1.0 0.4-0 .6 Glycol, mol / mol DDP 0.1-1.0 0.4-0.6 * The amount of dodecylphenol diluent oil is:
Generally about 200-300 g. The amount of low base sulfonate (if used) is 1% that of the alkylphenol.
It is about 10 to 20 g per mole.

The reaction to form a sulfurized alkaline earth metal alkyl phenate comprises, in the present invention, an alkaline earth metal, an alkylphenol, a solvent for a promoter, a lubricant diluent, and an optional low base sulfonate. Thirteen
7.8 to about 193.3 ° C (about 280 to about 380 ° F),
Preferably about 160.0 to about 182.2 ° C (about 320 to
It is carried out at a reaction temperature of about 360 ° F.) by contacting for a time sufficient to form the desired intermediate, usually about 40-80 minutes.

The reactor has a temperature of 137.8 to 193.3 ° C. (28
In order to avoid wasting time during reaching the desired reaction temperature of 0-380 ° F.), alkylphenol and alkaline earth metal bases are preferably passed across the preheater at the desired reaction temperature. At the same time as the reactor is fed, the promoter solvent is fed separately to the reactor. It is preferred not to feed the glycol solvent with the Ca (OH) ₂ and the alkylphenol across the preheater. This is because glycol will form a complex salt that will clog the preheater, typically the heat exchanger.

After the addition of the solvent of metal base, alkylphenol and promoter, sulfur is added to the reaction mixture at a rate slow enough to control the exotherm of the reaction and the generation of exhaust gas. When the alkylphenol and metal base are fed to the preheated reactor, slow sulfur addition (over a time period of 30-60 minutes) is important.

[0027] After formation of the sulfurized metal phenate intermediate as described above carbon dioxide reduction, in accordance with the present invention, further carbon dioxide of at to the same time the CO ₂ gas added to the reactor the solvent alkaline earth metal base and promoter Thereby, carbonic acid overbasing can be achieved. The stoichiometric range of reaction for carbon dioxide is as follows:

[0028]

Table 2 Range Preferred range Ca (OH) ₂ , mol / mol DDP * 0.5-2.0 1.0-1.5 Glycol, mol / mol DDP 0.5-2.0 1.0-1 .5 CO ₂ , mol / mol DDP 0.5-2.0 1.0-1.5 * dodecylphenol According to the invention, C of about 0.40: 1 to about 0.95: 1.
The molar ratio of O ₂ / alkaline earth metal base and the feed rate of the reaction components are controlled so as not to be substantially higher or lower than the rate at which the carbon dioxide reaction can proceed, An earth metal base, a promoter solvent and CO ₂ are fed to the reactor. If this rate is greater than the rate at which carbon dioxide can occur, the reaction mixture becomes very viscous, carbon dioxide is difficult to carry out due to the formation of glycol oxide complexes, and the resulting product is generally of poor quality. Would be inferior If the feed rate is less than the rate at which carbon dioxide can occur, the reaction cycle time will be unnecessarily long.

As an example, in the case of a commercial 3000 gallon stirred tank reactor, the alkaline earth metal (5
A suitable rate for feeding 480 TBN Ca (OH) ₂ slurry in W oil) is about 70-90 pounds / minute, a glycol feed rate is about 10-15 pounds / minute, and a suitable rate. CO ₂ supply rate is about 7000 SC
It was determined to be FH.

The molar ratio of the CO ₂ and alkaline earth metal bases fed to the reactor during the carbon dioxide step constitutes an important aspect of the invention. When the molar ratio of CO ₂ / metal base supplied is less than about 0.40, the quality reaction mixture became too and processing difficulties become viscous, and the resulting product is inferior to as evidenced by water-durable Will have. When the molar ratio is greater than 0.95, there is also the risk of overcarbonated product resulting in a hazy phenate product characterized by poor water endurance properties. CO ₂ / alkaline earth preferred feed ratio of the metal of about 0.75 to 0.85: 1.

The carbon dioxide conversion reaction is carried out from about 148.9 to about 1.
82.2 ° C (about 300 to about 360 ° F), preferably about 165.6 to about 176.7 ° C (about 330 to about 350 °).
It can be carried out in the temperature range of F). Preferably, the alkaline earth metal base (in 5W oil) is fed to the reactor across a preheater set to the desired reaction temperature for carbon dioxide.

After the alkaline earth metal base and glycol have been completely fed to the reactor, the CO ₂ feed is continued until the carbon dioxide reaction is complete. Complete "leakage" of the exhaust gas, i.e., the supplied CO ₂ is evidenced by a sharp increase in the exhaust gas reactor when no longer absorbed in the reaction medium. Generally, the exhaust gas of the reactor is 5000S
Completion appears to have occurred at 5 minutes after crossing CFH.

After carbonization, unreacted glycols and alkylphenols can be stripped from the overbased product. This is typically 204.4 ~
Performed under vacuum at 400-480 ° F (248.9 ° C) with a nitrogen purge. After stripping, the product is filtered to remove fine solids.

The overbased sulfurized phenates prepared according to the present invention are suitable as detergents / antioxidants for lubricating oils, especially oils used in marine diesel engines.

[0035]

Example I (Comparative) In this example, an overbased sulfurized alkaline earth metal alkylphenate is prepared using a batch process. Eighty gallons of 5W oil was fed into a commercial 3000 gallon stirred tank reactor. Then add 73 to the reactor.
00 lbs of 180 TBN slurry of calcium hydroxide dodecylphenol was fed. This slurry is 1
700 gallons of 5.0 wt% alkaline earth metal sulfonate in combination with 1740 lbs of Ca (OH) ₂ and 1 quart of commercially available defoamer, 18
Prepared in advance by producing a slurry with a TBN of 0 (total base number according to ASTM D-2896). Simultaneously with feeding the dodecylphenol calcium hydroxide slurry to the reactor, 7128 pounds of ethylene glycol was fed to the reactor. Then 1 reactor
21.1 ° C (250 ° F), at which point 1
150 lbs of melted sulfur was fed to the reactor. The reactor is then brought to a temperature of 165.6 ° C (330 ° F),
Hold at that temperature for 60 minutes to achieve formation of the sulfurized calcium phenate. Then 3260 pounds of 5
The first stage of carbonic overbasing was performed by feeding 480 TBN slurry of calcium hydroxide in W oil and 510 pounds of ethylene glycol to the reactor. A slurry of calcium hydroxide, 480 TBN, in 5W oil was prepared in advance by mixing 1240 gallons of 5W, 1 quart of defoamer and 4140 pounds of Ca (OH) ₂ in a suitable holding tank. did. 480T
After feeding a slurry of BN and additional glycol, the entire reaction mixture was stripped with 2000 SCFH N ₂ with nitrogen. After nitrogen stripping, the reaction mixture was treated with 7000 SCFH of CO ₂ until carbon dioxide was complete as indicated by a sharp increase in the reactor offgas.
It turned into carbon dioxide. When the first carbon dioxide stage was complete, a second feed (3260 lbs) of 480 TBN calcium hydroxide / 5W oil slurry and ethylene glycol (510 lbs) was introduced into the reactor and then stripped with nitrogen. , The second carbon dioxide conversion step was performed. The reaction mixture was carbonated again with 7000 SCFH CO ₂ until carbonization was complete as evidenced by a sharp increase in the flue gas leak. The reaction product was then stripped in a conventional manner to remove unreacted glycols and alkylphenols and then filtered to remove solid particles. The final product had the following properties: Calcium (wt%) 9.4; Sulfur (wt%) 3.0; Glycol (wt%) 0.1; Carbonate C (wt%) 1.7; TBN ( mgKOH /
g) 267; PM flash point 180 ° C. (35
6 ° F); viscosity (cSt, 100 ° C) 151; BS & W
(Volume%) 0.02.

Example II (Comparative) In this example, a sulfurized overbased calcium phenate was prepared in a continuous process using two 3000 gallon reactors in series. 176.7 ° C (350 °
The first reactor, controlled at F), was charged with 32 lbs / min of 270 TBN calcium hydroxide dodecylphenol slurry, 3.4 lbs / min of ethylene glycol and 4.9 lbs / min of sulfur. Also 176.7 ° C
A second reactor controlled at (350 ° F.), reactor effluent from the first reactor via control level, 330 TBN calcium hydroxide dodecylphenol slurry at 46 lbs / min, 9.6 lbs. / Min of ethylene glycol and 2300 SCFH of CO ₂ were fed. The effluent from the second reactor was transported via a level control for stripping and filtration. The final product had the following properties: Calcium (wt%) 9.4; Sulfur (wt%) 3.2; Glycol (wt%) 0.1; Carbonate C (wt%) 1.3; TBN.
(MgKOH / g) 254; PM flash point (flash)
176.7 ° C (350 ° F); viscosity (cSt, 100
C.) 275; BS & W (% by volume) <0.05.

Example III In this example, overbased calcium sulfide dodecylphenol was prepared according to the present invention. A commercial 3000 gallon stirred tank reactor was charged with 80 gallons of 5W oil. 7300 lbs of 180 TBN calcium hydroxide dodecylphenol slurry (see preparation of slurry in Example I above) at 165.6 ° C (330 ° F).
It is supplied to the reactor through a preheater set to, and the temperature of the slurry is adjusted to 165.6 ° C. (330 ° C.) immediately before introduction into the reactor.
F). At the same time, but separately, 728 pounds of ethylene glycol was fed to the reactor. Molten sulfur was then fed into the reactor at a rate of 29 lbs / min until a total of 1150 lbs was fed. After the 180 TBN slurry feed, 50 gallons of 5W oil was added to the reactor through the same line used to feed the slurry. The reaction mixture was then held at 165.6 ° C (330 ° F) for 30 minutes to achieve formation of the sulfurized calcium dodecylphenate intermediate. A 480 TBN calcium hydroxide / 5W oil slurry (see Example I for slurry preparation) was then run across the second preheater set at 165.6 ° C (330 ° F) and a total of 6250 pounds of slurry. Carbonation of the intermediate was carried out by feeding the reactor at a feed rate of 82 lbs / min until it was fed. A 480 TBN slurry was fed and then 50 gallons of 5W oil was fed to the reactor through the same line used to feed the slurry.
Simultaneously with the feed of 480 tbh Ca (OH) ₂ / 5W oil slurry, 1020 pounds of ethylene glycol were fed separately at a rate of 13 pounds / minute and carbon dioxide gas was fed separately at a rate of 7000 SCFH. 480 TB
After the completion of the N slurry and the glycol supply, the CO ₂ supply was continued until the carbon dioxide conversion was completed. Carbon dioxide was considered complete 5 minutes after the reactor offgas exceeded 5000 SCFH. The product is 248.9 ° C
After vacuum stripping with nitrogen at (480 ° F) and filtering through Celite 535, it had the following final properties: calcium (wt%).
9.4; Sulfur (wt%) 2.9; Glycol (wt%)
0.6; carbonate C (% by weight) 1.8; TBN (m
gKOH / g) 272; PM flash point (flash) 18
2.2 ° C (360 ° F); viscosity (cSt, 100 ° C) 1
06; BS & W (% by volume) <0.05.

Batch Preparation of Example I and Example II
A comparison of reaction cycle times for the production of the batch process of the invention described in I is set forth in Table I.

[0039]

Table I Comparison of reaction cycle times for Example I and Example III Process Example Example I Example III (min) 1. Feed 5W oil, glycol and 180 TBN Ca (OH) ₂ in dodecylphenol slurry 65 65 2. Supplying sulfur 15 60 3. 3. Heat reactor to 165.6 ° C for sulfurization reaction 120-180 0 4. Retention of reaction 60 30 5.5 Feed a slurry of 480 TBN of Ca (OH) ₂ in 5.5 W oil and glycol 40 80 6. Stripping with N ₂ 20 7. Carbon dioxide conversion until exhaust gas leaks 60 40 8. Repeating steps 5-7 120 0 reaction cycle time (min) 500-560 275 Both preparations treat the same amount of reaction components to yield essentially equal amounts and quality of product, but Example III The improvement of the present invention carried out at a reaction cycle time of 225
It decreased by 285 minutes. This significant reduction is made possible by a novel and unclear method in which the steps of sulfidation and carbon dioxide are carried out in the batch process of the invention. In particular, carbon dioxide of the two stages that are required in a batch process of Example I, in the present invention, at the same time carbon dioxide reduction and to supply the slurry and glycol Ca (OH) ₂ / 5W oil 480TBN reactor Are eliminated by carrying out. This feature of the invention is described in Example II while avoiding the problem of high viscosity in the batch reaction mixture, which problem requires two stages of carbon dioxide as used in Example I. It avoids the problem of excessive carbonation or undercarbonation associated with continuous processes such as that which creates difficulties with water durability in the phenate product.

The water durability of the overbased phenate prepared in Example II (continuous method) was compared to the water durability of the overbased phenate prepared according to the invention described in Example III. Normal processing levels of two phenates containing a major proportion of lubricating oil and a small effective amount of ashless dispersant, low base calcium sulfonate, high base magnesium sulfonate, antioxidant and zinc dialkyldithiophosphate. Was incorporated into a standard commercial lubricating oil formulation. The water durability of the standard formulation containing the overbased phenate of Example II was compared to that of the standard formulation containing the overbased phenate of Example III, where 21.1 ° C. (70 ° F) or 54.4 ° C
Measure haze and sedimentation in a sample of the formulation after storage for 6 weeks at (130 ° F) and three different water levels in the formulation (0.10, 0.15 and 0.20 wt%). did. Thus, 6 separate samples of the standard formulation were tested for each overbased phenate. The water durability test results are summarized in Table II below.

[0041]

Table II Table II Water endurance test of phenates of Examples II and III Storage at 21.1 ° C Stored water at 54.4 ° C , wt% grade ** Water, wt% grade 0.10 0.15 0.20 0.10 0.15 0.20 Example II A / tr * A / tr M / 15 Excellent A / tr M / 15 M / 20 Boundary Example III A / tr A / tr A / tr Ideal A / tr A / tr M / 20 Immediate * Haze / settling; haze ratings start with "A" for best clarity and grades of "D" or higher are considered failed. Sedimentation is measured in% by volume, and "tr" means trace sedimentation. Sedimentation> 1% at any time during 6 weeks of storage fails.

** Grades are assigned as follows: Grade Criteria Ideally no clouding or settling at any water level Excellent 0.20% failing clouding or settling in water Boundary line 0.15% Failed haze or settling in water Poor 0 15% Failed haze or settling in water As the data set forth in Table II above demonstrate, the method of the present invention (Example III) is similar to that of Example II. It produces an overbased phenate with significantly improved water durability over the overbased phenate produced in a continuous process.

In view of the data presented in Tables I and II, the method of the present invention is capable of significantly increasing the throughput of batch processes while at the same time providing the excellent water normally associated with batch process manufacture. Achieve durability characteristics.

The main features and aspects of the present invention are as follows.

1. Steps: a) feeding into the reactor a preheated mixture consisting essentially of an alkaline earth metal base and an alkylphenol in a molar ratio of 0.1: 1 to 1.0: 1, wherein said mixture is 137.8-193.3 ° C (280-38) in the reactor.
0 ° F.) at a temperature in the range of 0.1 to 1.0 moles of promoter solvent per mole of alkylphenol in the reactor at the same time, but separately. Then, b) the reaction temperature was set at 137.8 to 193.3 ° C (280 to 3).
20 to 180 at a rate that controls the heat generation of the reaction and the generation of exhaust gas while maintaining the temperature within the range of 80 ° F.
1.0 to 2.0 moles of molten sulfur per mole of alkylphenol are fed into the reactor over a period of minutes, and c) when the sulfur feed is complete, 137.8. ~ 193.
Allowing the contents in the reactor to interact for a time sufficient to form a sulfurized alkaline earth metal alkylphenate at a reaction temperature in the range of 3 ° C. (280-380 ° F.), d) reaction temperature 137.8-193.3 ° C (280-3
Maintained at a temperature of 80 ° F.), at a controlled feed rate that is substantially less than or less than the rate at which the reaction components present in the reactor react to form the overbased phenate. (I) 0.5 to 2 moles of alkaline earth metal base per mole of alkylphenol, (ii) 0.5 per mole of alkylphenol.
By simultaneously feeding into said reactor 0.40 to 0.95 mol of carbon dioxide gas per mol of ˜2.0 mol of promoter solvent and (iii) alkaline earth metal base. Converting the sulfurized alkaline earth metal alkyl phenate to an overbased phenate, and e) when the supply of alkaline earth metal base and promoter solvent to the reactor is complete, the carbon dioxide supplied is the reaction medium. When it is no longer absorbed in the reactor, the carbon dioxide supply is continued until the completion of the carbonation reaction as evidenced by a sharp increase in the exhaust gas in the reactor, f) under vacuum 204.4-248. 9 ° C (400-48
At temperatures in the range of 0 ° F), unreacted alkylphenol and promoter solvents are removed with an inert gas purge, and g) the resulting reaction product mixture is filtered and the filtered product is recovered. A method of producing an overbased sulfurized alkaline earth metal alkylphenate having excellent water durability properties in a lubricating oil formulation, the method comprising: performing a reaction cycle time of 6 hours or less. And wherein the filtered product has water endurance properties normally associated with batch production of the product in a process having a reaction cycle time of at least 8 hours.

2. The process of claim 1 wherein the alkaline earth metal base is calcium hydroxide, the alkylphenol dodecylphenol, and the promoter solvent is ethylene glycol.

3. The molar ratio of calcium hydroxide / dodecylphenol in step (a) is 0.4 to 0.6: 1 and the molar ratio of ethylene glycol / dodecylphenol in step (a) is 0.4 to 0.6: 1. And the molar ratio of sulfur / dodecylphenol in the step (b) is 1.3 to 1.6: 1, and the molar ratio of calcium hydroxide / dodecylphenol in the step (d) is 1.0 to
1.5: 1 and the ethylene glycol / dodecylphenol molar ratio in step (d) is 1.0 to 1.5:
1, and the molar ratio of CO ₂ / dodecylphenol provided in step (d) and (e) 1.0
The method according to paragraph 2 above, which is 1.5: 1.

4. The reaction temperature in steps a), b), c) and d) is 148.9 to 182.2 ° C (300 to 3).
The method of claim 1 wherein the temperature is maintained within the range of 60 ° F.

5. CO ₂ / supplied in step d)
The method of claim 1 wherein the alkaline earth metal base is 0.75-0.85: 1.

6. The method according to claim 1, wherein the alkaline earth metal base is an oxide or hydroxide of calcium or magnesium.

7. The process of claim 1 wherein the reaction of step c) is carried out in the presence of a low base alkaline earth metal sulfonate.

8. Wherein the sulfonate is a calcium alkylbenzene sulfonate having an alkyl substituent in the range of C ₁₅ -C _80, and a base of an alkaline earth metal is calcium base, the method of the seventh Claims.

9. The process of claim 1 wherein the reactions of steps c) and d) are carried out in the presence of a lubricating oil reaction diluent.

10. The alkaline earth metal base is an alkaline earth metal oxide or hydroxide and the promoter solvent is ethylene glycol, and the reaction temperature in steps a), b), c) and d) is 148.9. ~ 182.2 ° C
(300-360 ° F.), the reaction of step c) is carried out in the presence of a low base alkali metal sulfonate, and the reactions of steps c) and d) are a mineral lubricating oil reaction diluent. And the CO ₂ / oxide or hydroxide ratio fed in step d) is 0.75.
The method of claim 1, wherein the ratio is ˜0.85: 1.

11. The alkaline earth metal base is a calcium base and the alkali metal sulfonate is a C ₁₅
A calcium alkylbenzene sulfonate having an alkyl substituent in the range of -C _80, the method of the paragraph 10, wherein.

12. Calcium base is calcium hydroxide, and the alkyl substituent is derivatized from C ₂ -C ₄ monomers of the polymer, the method of the claim 11 wherein.

13. The method according to the above item 11, wherein the alkylphenol is dodecylphenol.

14. The calcium hydroxide / alkylphenol molar ratio in step a) is 0.4 to 0.6: 1 and the ethylene glycol / alkylphenol molar ratio in step a) is 0.4 to 0.6: 1, The ethylene glycol / alkylphenol molar ratio in a) is 0.4-0.6: 1 and the sulfur / alkylphenol molar ratio in step b) is 1.3-1.
6: 1, the calcium hydroxide / alkylphenol molar ratio in step d) is 1.0-1.5: 1 and the ethylene glycol / alkylphenol molar ratio in step d) is 1.0-1.5. : 1, and step d) and the molar ratio of CO ₂ to be supplied in e) is 1.0 to 1.5: 1, the method of the claim 11 wherein.

15. 15. The method according to the above item 14, wherein the alkylphenol is dodecylphenol.

Claims (1)

[Claims] 1. A step: a) feeding into the reactor a preheated mixture consisting essentially of an alkaline earth metal base and an alkylphenol in a molar ratio of 0.1: 1 to 1.0: 1, Here, the mixture was added to the reactor at 137.8 to 193.3 ° C (280 to 38 ° C).
0 ° F.) at a temperature in the range of 0.1 to 1.0 moles of promoter solvent per mole of alkylphenol in the reactor at the same time, but separately. Then, b) the reaction temperature was set at 137.8 to 193.3 ° C (280 to 3).
20 to 180 at a rate that controls the heat generation of the reaction and the generation of exhaust gas while maintaining the temperature within the range of 80 ° F.
1.0 to 2.0 moles of molten sulfur per mole of alkylphenol are fed into the reactor over a period of minutes, and c) when the sulfur feed is complete, 137.8. ~ 193.
Allowing the contents in the reactor to interact for a time sufficient to form a sulfurized alkaline earth metal alkylphenate at a reaction temperature in the range of 3 ° C. (280-380 ° F.), d) reaction temperature 137.8-193.3 ° C (280-3
Maintained at a temperature of 80 ° F.), at a controlled feed rate that is substantially less than or less than the rate at which the reaction components present in the reactor react to form the overbased phenate. (I) 0.5 to 2 moles of alkaline earth metal base per mole of alkylphenol, (ii) 0.5 per mole of alkylphenol.
By simultaneously feeding into said reactor 0.40 to 0.95 mol of carbon dioxide gas per mol of ˜2.0 mol of promoter solvent and (iii) alkaline earth metal base. Converting the sulfurized alkaline earth metal alkyl phenate to an overbased phenate, and e) when the supply of alkaline earth metal base and promoter solvent to the reactor is complete, the carbon dioxide supplied is the reaction medium. When it is no longer absorbed in the reactor, the carbon dioxide supply is continued until the completion of the carbonation reaction as evidenced by a sharp increase in the exhaust gas in the reactor, f) under vacuum 204.4-248. 9 ° C (400-48
At temperatures in the range of 0 ° F), unreacted alkylphenol and promoter solvents are removed with an inert gas purge, and g) the resulting reaction product mixture is filtered and the filtered product is recovered. A method of producing an overbased sulfurized alkaline earth metal alkylphenate having excellent water durability properties in a lubricating oil formulation, the method comprising: performing a reaction cycle time of 6 hours or less. And wherein the filtered product has water endurance properties normally associated with batch production of the product in a process having a reaction cycle time of at least 8 hours.