JP3513771B2 - Method of overbased phenate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to a salt of an alkaline earth metal.
Groups, sulfur and alkylphenols are first mutual solvents
To form an intermediate of sulfurized metal phenate
And then intermediate this intermediate with additional alkaline earth metal salts.
Overbased by carbonation in the presence of groups, overbased
Producing sulfided alkaline earth metal alkyl phenates
About the method. In particular, the present invention_Two/ Alkaline earth
CO on magnetic tape with specified base_TwoThe reactor
Introduced simultaneously with the introduction of the alkaline earth metal base,
By performing the carbonization process in a single step,
A batch process that substantially increases throughput. [0002] Lubricants are today's diesel and automotive
Tend to degrade under the normal conditions encountered in engines
is there. Sludge, lacquer and resinous material form,
Engine parts, especially piston rings, grooves and slots
Sticking to the cart, these are the engine efficiency, operation and
May have detrimental effects on useful life. Normally,
Additives are mixed into the lubricating oil to reduce the formation of such substances.
Diminish and keep them suspended, thus
Parts are kept clean and operation is properly maintained.
Additives that reduce the tendency of lubricating oils to form oxidation products
Is called an antioxidant, but suspends oxidation products and sludge.
Turbid or produce such from engine parts
Cleans or disperses additives that tend to clean
Called agent. Certain additives are used in antioxidants and detergents.
It is not unusual to have both properties. [0003] Overbased sulfurized alkaline earth metal alkyl
Zeneate provides oxidation control and detergency in lubricating oils.
Found to be particularly useful for the dual purpose of providing
Was done. [0004] The term "overbased" refers to phenate substances
Large amount of alkaline earth in excess of that required for neutralization
It means the fact that it incorporates a metal base. Typically
Means that the overbased phenate has about 100-400 TBN
(Total number of bases). Such high salt
Adds harmful acids formed during engine combustion
The agent can be neutralized and converted to carbon dioxide (carbon)
cation) or carbonate overcarbonate (carbonate)
  well-known (usually called overbasing)
Achieved using technology. This technique is generally comparable
Alkaline earth gold with very low levels of metal base
Including the formation of a sulfurized phenate intermediate of the genus. Then this
The intermediate is treated with an excess of additional alkaline earth metal. Yo
In poorly understood reactions, sulfurized metal phenates
Excess metal salt in an appropriate solvent, usually glycol
By blowing gaseous carbon dioxide into the
And let it react. CO_TwoTreatment or carbonation
A fine colloidal dispersion is formed, which results in excess gold
The genus bases essentially “dissolve”. [0005] In a batch or continuous process, the overbased sulfurized
Producing a rukari earth metal alkyl phenate comprises:
It is well known in the art. For processing of both types
There are significant advantages and disadvantages associated therewith. For example, the batch method, as expected,
It takes more time to manufacture than when using the continuous method.
The main disadvantage is that the amount of product that can be produced is very small.
Have. Nevertheless, the very significance of batch methods
The tasting advantage is that the bottom of carbon dioxide is very closely and
That it can be controlled with reliability.
And This is important. Because of the overbased
Excessive or insufficient carbonation of nates
Is a serious problem. Excessively carbonized
The resulting product generally has poor water resistance in lubricating oil formulations.
Shows the durability and destroys the colloidal dispersion described above.
Cloudy Products with insufficient carbon dioxide increase viscosity
Poor filterability and difficult to remove glycol
You. Batching avoids these problems and, in particular,
The choice if durable phenate is an important purpose
Is the law. [0007] Continuous processing maximizes production throughput.
Has the advantage of However, in a continuous way
And typically, the initial metal sulfide using the first reactor
The formation of the phenate intermediate is carried out but in the second reactor or
Uses a series of continuous reactors for carbon dioxide conversion
I do. A well-known phenomenon associated with the continuous method is the dwell time
It is that of the distribution between. This phenomenon is a continuous phenate method
It is particularly harmful in the carbon dioxide conversion process. Why
Et al., It is over-carbonated phenate and
Because it forms both phenates that are under-carbonized
is there. For this reason, overbased filters produced in a continuous process
The phenate is significantly better than the batch-produced phenate.
Poor water durability generally results. Phenomenon of residence time distribution
Increases the number of reactors used for carbon dioxide
To minimize plug flow by mimicking the reactor.
But with substantial capital expenditures. [0008] Ideally, the throughput and throughput of a continuous process production
And carbon dioxide control provided by the batch method
With excellent water durability.
It is desirable to obtain a phenate. Overbased sulfurized alkaline earth metal alkyl
Numerous patents relating to the production of carbonates are produced. bell
Ghi patent 876,119 is the most relevant,
Sulfurized overbased alkaline earth metal alkyl phenate
A method for fabricating the same, wherein the method comprises:
Group metal base, alkylphenol and mutual solvent
For a time sufficient for the formation of metal phenate in the heat exchanger
Contact and then react the phenate without substantial cooling.
Reaction zone where the metal phenate reacts
Contact with sulfur under conditions to form sulfurized metal phenates
The formation of a sulfurized metal phenate intermediate
To achieve. This intermediate is then converted to CO 2_TwoCarbon dioxide
Can be This patent describes a "quasi-batch" method.
Where the reaction components are placed in the reactor while the reaction is taking place.
This patent describes the invention of carbon dioxide
Teaching or suggesting the unique means employed in
Not in. A general object of the present invention is to provide improved production.
Same as producing overbased metal phenate with throughput
Provides a batch method without the drawbacks sometimes associated with continuous methods
It is to be. Other objectives will be apparent to those skilled in the art thereafter.
Will. The present invention comprises the steps of:
Solvents for alkylphenol, sulfur, accelerator, etc. in the reactor
A mixture consisting essentially of an alkaline earth metal base
Contact with a sulfurized alkaline earth metal alkyl phenate
And then (b) under the reaction conditions (i) alkaline earth
A metal-like base, (ii) a solvent for the promoter and (iii)
Carbon dioxide from about 0.40: 1 to about 0.95: 1
Carbon / alkali earth metal base molar ratio and carbon dioxide
Element, alkaline earth metal base and alkaline earth gold sulfide
Substantially greater than the rate at which the genus alkylphenate reacts
Not too slow or not controlled speed
At the same time and react in it.
And the alkaline sulfide earth formed in (a) above
Overbasing the metalloid alkylphenate and (c)
Alkaline earth metal compound and accelerator to reaction zone
When the supply of the solvent is completed, before the reaction is completed,
Continue the supply of carbon dioxide
A method for producing an alkaline earth metal alkyl phenate.
You. In a related aspect, the invention further provides
Step: (a) molar ratio of about 0.1: 1 to about 1.0: 1
Alkaline earth metal bases and alkylphenols at low temperatures
The mixture consisting essentially of
Where the mixture is about 137.8-193.3.
Reactor preheated to a temperature of about 280-380 ° F
Into the reactor, at the same time, alkyl
About 0.1-1.0 mole promotion per mole of phenol
The solvent for the agent is fed, and then (b) the reactor is brought to about 137.8.
While maintaining at ~ 193.3 ° C (about 280-380 ° F)
The reaction takes about 20 to 180 minutes.
In a vessel, add about 1.0 per mole of alkylphenol.
To about 2.0 mol of sulfur, and (c) the supply of sulfur is complete.
When sintering, at the above reaction temperature, alkaline earth gold sulfide
Of sufficient time to form the genus alkylphenate
While the contents in the reactor interact, (d) about 13
7.8 to about 193.3 ° C (about 280 to about 380 ° F)
At temperature, the reactants present in the reactor react
Substantially greater than the rate at which overbased phenates are formed
Not controlled or not small supply
At a rate of (i) about 1 mole per mole of alkylphenol
0.5 to about 2.0 moles of an alkaline earth metal base, (i
i) about 0.5 to about per mole of alkylphenol
2.0 moles of promoter solvent and (iii) alkaline earth
About 0.40 to about 0.95 moles per mole of a class of metal bases
Of carbon dioxide gas into the reactor at the same time
And reacting in it, the alkali sulfide
Converts earth metal alkyl phenates to overbased phenates
(E) dissolution of the base and promoter of the alkaline earth metal
When the supply of the medium to the reactor is completed,
Continue supplying carbon dioxide until the reaction is complete,
Overbased sulfurized alkaline earth metal alkylphenates
And a method for producing the same. Although the present invention can be considered as a batch method,
The carbon dioxide conversion method used in this method is a reaction cycle.
This method significantly reduces the
Reach or equal production throughput
be able to. Around alkylphenols and metal bases
Feed at ambient temperature and allow the reactor to reach the desired reaction temperature.
In the related aspect above, as opposed to waiting to be heated
The sulfurization process uses preheating means as required by
Reaction temperature of alkylphenol and metal base in reactor
More than the reaction cycle time, if introduced in degrees
Reduction can be achieved. Using the method of the present invention
Overbased phenates produced by
It has excellent water durability characteristics and
The process is performed during a typical 9-10 hour batch reaction cycle.
The time can be reduced as much as 4-5 hours. In general, the method of the present invention is a single commercial scale
It can be carried out in two stages in a stirred tank reactor
it can. In the first step, a suitable alkyl
Promotes ruphenate, alkaline earth metal base and sulfur
Contact in the presence of a promoter or mutual solvent.
To obtain a sulfurized alkaline earth metal alkylphenate intermediate
Form. In the second step (carbonation) of this method
And add an additional amount of alkaline earth metal sulfide intermediate
CO in the presence of a metal base and a promoter solvent_TwoWith gas
To process. Some kind of one or both of these steps
By making changes, the invention provides an overbased phenate
The reaction capacity required to produce a finished batch of product
Dramatically reduces cycle time. Each of the two steps here
This will be described in detail. [0015]Formation of sulfurized metal phenate intermediate At the front end of the method of the present invention, an alkylphenol,
The presence of bases and sulfur promoters for alkaline earth metals.
React below to form the sulfurized metal phenate. Alkyl phenols useful in the present invention
Is the formula R (C₆H_Four) OH, where R is 8-40;
Preferably a straight chain having 10 to 30 carbon atoms or
Is a branched alkyl group and the moiety (C₆H_Four)
Is a benzene ring. An example of a suitable alkyl group is Octyl
Le, decyl, dodecyl, tetradecyl, hexadecyl
What is it? The alkaline earth metal base is calcium,
Barium, magnesium and strontium.
Calcium and magnesium are preferred. Most commonly
The bases used are oxides and hydroxides of the above metals,
For example, calcium oxide, calcium hydroxide, burr oxide
And magnesium oxide. Calcium hydroxide
Is commonly called hydrated lime,
Most commonly used in the manufacture of products and during storage
Excellent quality without degradation (relatively free of carbonates)
It is preferable to use the hydrated lime of (i). [0018] The accelerator solvent is also sometimes referred to as a co-solvent.
Base, alkaline earth metal base, alkylphenol and
Perceived by both sulfide and sulfide metal phenate intermediates
Can be any stable organic liquid with solubility of
it can. A wide variety of molten sulfur is used in this field
It is known that many such suitable sintered bodies are
Recall and glycol monoethers, such as ethyl
Len glycol, 1,4-butanediol, ethylene glycol
Derivatives of recol, for example, monomethyl ether, mono
Ethyl ether and the like. vic-glycol is preferred
And ethylene glycol activates the neutralization reaction
Most effective and neutralizing
The exact characteristics that describe the function are not known.
Not. The sulfur used in this reaction is elemental sulfur.
It is yellow. In the present invention, the use of molten sulfur
And was found to be desirable. In the present invention, the formation of sulfurized phenate
Of low base alkylbenzene sulfo
It is more desirable to use phosphates, but this is required
Not done. Suitable sulfonates for use include, for example,
Fin or chain length C₁₅-C₈₀C_Two-C_FourOlefin port
Alkyl-benzene sulfone derivatized from limmer
Having a molecular weight of preferably 400 or less obtained by
Fonic acid and alkaline earth metals such as calcium,
Salts such as barium and magnesium. Of this description
In the following examples, polypropane having a chain length of about C-60
Of low-base calcium sulfonate produced from
Included in the reaction. In addition to the above reaction components, metal sulfide phenene
Formation is preferably performed in the presence of a lubricating oil reactive diluent
I do. The lubricating oil contains the phenate produced according to the present invention.
Any lubrication used in the final lubricating oil formulation having
Oils such as naphthenic bases, paraffin bases and mixed
5W, 10W or event including combined base mineral oil
It can be 40W oil. 5W oil as reaction diluent
Generally the most appropriate. The stoichiometric amount of the reaction for the above reactants
The range of is as follows: [0023] [Table 1]range Preferred range Sulfur, mol / mol DDP * 1.0-2.0 1.3-1.6 Ca (OH)_Two, Mol / mol DDP 0.1-1.0 0.4-0.6 Glycol, mol / mol DDP 0.1-1.0 0.4-0.6 * Dodecyl phenol The amount of diluent oil is
Generally about 200-300 g. Low base sulfone
The amount of the acid salt (if used) is
About 10 to 20 g per mole. Sulfated alkaline earth metal alkyl phenates
In the present invention, the reaction to form
Genus, alkylphenol, accelerator solvent, lubricating oil dilution
Agent, and any low base sulfonate, to about 13
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
At a reaction temperature of about 360 ° F., the desired intermediate form
Contact for a sufficient time, usually about 40 to 80 minutes.
It is implemented by doing. The reactor is operated at 137.8-193.3 ° C. (28
0-380 ° F.) during the desired reaction temperature
Alkylphenol and
The alkaline earth metal base is preferably treated at the desired reaction temperature.
At the same time as feeding the reactor across the set preheater
The promoter solvent is fed separately to the reactor. Glycol solution
The medium is Ca (OH)_TwoWith alkylphenol
It is preferred not to feed across the preheater. Why
Glycol clogs preheaters, typically heat exchangers
This would form a complex salt that would cause Metal bases, alkylphenols and promoters
After the addition of the agent solvent, sulfur is added to the reaction mixture as the reaction exotherms.
Slow enough to control emissions and emissions
Add at a slow rate. Alkyl phenols and metal bases
Is supplied to the preheated reactor,
The addition of yellow (which takes 30-60 minutes) is important
You. [0027]Carbon dioxide After the formation of the sulfurized metal phenate intermediate as described above,
In accordance with the invention, further alkaline earth metal base and promotion
The solvent for the agent is added to the reactor while_TwoDiacid in gas
Carbonization to achieve carbonic acid overbasing.
Can be. Stoichiometric amount of reaction for carbonation
The range of is as follows: [0028] [Table 2]range Preferred range Ca (OH)_Two, Mol / mol DDP * 0.5-2.0 1.0-1.5 Glycol, mol / mol DDP 0.5-2.0 1.0-1.5 CO_Two, Mol / mol DDP 0.5-2.0 1.0-1.5 * Dodecyl phenol According to the present invention, a C of about 0.40: 1 to about 0.95: 1.
O_Two/ Mole ratio of alkaline earth metal base and reactant
Supply rate can advance the carbon dioxide conversion reaction
Not substantially higher or lower than speed
Alkaline earth metal salts at a controlled rate
Groups, promoter solvents and CO_TwoTo the reactor. This
Is greater than the rate at which carbonation can occur
The reaction mixture becomes very viscous if
It is difficult to perform carbon dioxide due to formation of oxide complex
And the resulting product will generally be of poor quality
U. Feed rate is the rate at which carbonation can occur
If smaller, the reaction cycle time will be unnecessarily long.
You. As an example, a commercial 3000 gallon stirrer
Alkaline-earth metal (5
480 TBN Ca (OH) in W oil_TwoSlurry shape
Suitable speeds for feeding the state) are about 70 to 90 pounds / minute.
And the glycol feed rate is about 10-15 pounds per minute.
Yes and suitable CO_TwoSupply speed of about 7000SC
It was determined to be FH. CO_TwoAnd alkaline earth metal bases
The molar ratio fed to the reactor during the carbon oxide
Constitute an important aspect of Ming. CO supplied_Two/ Metal base
The reaction mixture is viscous if the molar ratio of
And becomes difficult to process, and the resulting product is
Poor quality as evidenced by water intolerance
Will. If the molar ratio is greater than 0.95,
Cloudy phenate raw material characterized by poor water endurance properties
The danger of excessively carbonized products
Exists. CO_Two/ Preferred supply ratio of alkaline earth metal
Is about 0.75 to 0.85: 1. The carbonation reaction is carried out at 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). Preferred
Or alkaline earth metal base (in 5W oil) with carbon dioxide
Reaction across preheater set to desired reaction temperature for
Supply to vessel. Alkaline earth metal bases and glycols
Is completely supplied to the reactor, and the carbon dioxide conversion reaction is complete.
Until tied, CO_TwoContinue to supply. Completion of exhaust gas
"Leakage", that is, the supplied CO_TwoIs in the reaction medium
Sharp increase in reactor exhaust when no longer absorbed
More proven. Generally, the exhaust gas of the reactor is 5000S
In 5 minutes after the CFH was over, the conclusion was thought to have taken place.
Is After carbonation, unreacted
And glycol and alkylphenol
Can be removed. This is typically 204.4-
At 400-480 ° F (248.9 ° C), the nitrogen
Performed under vacuum. After stripping, the product
To remove fine solids. The overbased sulfided sulfur produced according to the present invention
Nate is used in lubricating oils, especially in marine diesel engines.
Suitable as a cleaning agent / antioxidant for used oils
That's right. [0035] 【Example】Example I (Comparative) In this example, overbased alkaline sulfide
Production of metal-class alkyl phenates using a batch process
You. 80 gallons of 5W oil with commercial 3000 gal agitation
Was fed into the tank reactor. Then, 73
00 pounds 180 TBN calcium hydroxide dodecyl
A slurry of phenol was fed. This slurry contains 1
700 gallons of 5.0% by weight alkaline earth metal sulfo
1740 pounds of Ca (OH)_TwoAnd one quo
In combination with the commercially available antifoaming agent
TBN of 0 (total bases according to ASTM D-2896)
By producing a slurry having
Prepared. Dodecylphenol calcium hydroxide slurry
7128 pounds of ethyl
The glycol was fed to the reactor. Then, the reactor was
21.1 ° C. (250 ° F.), at which point 1
150 pounds of molten sulfur were fed to the reactor. Next
Bring the reactor to a temperature of 165.6 ° C. (330 ° F.)
Then hold at that temperature for 60 minutes to
Achieve the formation of the nate. Then 3260 pounds of 5
480 TBN slurry of calcium hydroxide in W oil
And 510 pounds of ethylene glycol to reactor
To carry out the first stage of carbonation overbasing
Was. 1240 gallons of 5 W, 1 quart of defoamer and
4140 pounds of Ca (OH)_TwoIn a suitable holding tank
Calcium hydroxide in 5W oil by mixing
A slurry of 480 TBN was prepared previously. 480T
After feeding BN slurry and additional glycol,
Of the reaction mixture of 2000 SCFH with N_TwoWith nitrogen
Tripped. After nitrogen stripping, the reactor
CO2 conversion as shown by the sharp increase in exhaust gas
Until complete, the reaction mixture is brought to 7000 SCFH CO 2_Two
To convert to carbon dioxide. The first carbonation stage is complete
Sometimes the second supply (3260 pounds) of 480 TBN hydroxyl
Slurry of calcium fluoride / 5W oil and ethylene glyco
(510 pounds) into the reactor and then with nitrogen
The second carbon dioxide conversion by stripping
The process was carried out. Proof by sharp increase in exhaust gas leakage
Reaction mixture until carbonization is complete as indicated
The product is again 7000 SCFH CO_TwoTo carbon dioxide
Was. The reaction product is then stripped in the usual way.
To remove unreacted glycol and alkylphenol
And then filtered to remove solid particles. Final product
Had the following properties: calcium (% by weight) 9.4;
Yellow (% by weight) 3.0; glycol (% by weight) 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
(% By volume) 0.02. [0036]Example II (Comparative) In this example, sulfurized overbased calcium
Reaction of two 3000 gallons of phenate in a continuous manner
The vessels were manufactured in series. 176.7 ° C (350 °
32 lb / min into the first reactor controlled in F)
270 TBN calcium hydroxide dodecylphenols
Rally, 3.4 lb / min ethylene glycol and
4.9 lb / min of sulfur was fed. 176.7 ° C
(350 ° F) in the second reactor
The flow of the reactor from the first reactor via the control
Deposit, 330 TBN calcium hydroxide at 46 lb / min
Mudodecyl phenol slurry, 9.6 lb / min
Tylene glycol and CO of 2300 SCFH_TwoProvide
Paid. Level control of effluent from the second reactor
Transported for stripping and filtration through
Was. The final product had the following properties: calcium (weight
%) 9.4; sulfur (% by weight) 3.2; glycol (% by weight)
%) 0.1; carbonate C (% by weight) 1.3; TBN
(Mg KOH / g) 254; PM flash point (flash)
350 ° F .; viscosity (cSt, 100
° C) 275; BS & W (% by volume) <0.05. [0037]Example III In this example, the overbased calcium dodecyl sulfide
Phenol was prepared according to the present invention. Commercial 3000 ga
Supply 80 gallons of 5W oil to Ron's stirred tank reactor
did. 7,300 pounds of 180 TBN calcium hydroxide
Mudodecylphenol slurry (as in Example I above)
Slurry) (330 ° F) at 165.6 ° C (330 ° F).
To the reactor through the preheater set to
Immediately before the introduction of the slurry, the temperature of the slurry was increased to 165.6 ° C (330 ° C).
F). At the same time, but separately, 728 pounds
Ethylene glycol was fed to the reactor. Then sum
Reacts molten sulfur until 1150 pounds are supplied
The vessel was fed at a rate of 29 pounds / minute. 180 TBN
After supplying slurry, same as used for supplying slurry
50 gallons of 5W oil to the reactor through the line
Was. The reaction mixture was then brought to 165.6 ° C (330 ° F).
Hold for 30 minutes, calcium sulfide dodecylphenate
Intermediate formation was achieved. Next, 480 TBN of hydroxyl
Calcium fluoride / 5W oil slurry (Slurry preparation
(See Example I) at 165.6 ° C (330 ° F).
6250 lbs across the 2nd preheater
82 pounds / minute until the slurry of
By feeding the reactor at the feed rate, the intermediate
A carbon oxide conversion was performed. Supply 480 TBN slurry
And then use the same laser used to supply this slurry.
50 gallons of 5W oil was fed to the reactor through the reactor.
480 tbh of Ca (OH)_Two/ 5W oil slurry supply
At the same time, separately 1020 pounds of ethylene glycol
At a rate of 13 lbs / min and separate carbon dioxide
Gas was supplied at a rate of 7000 SCFH. 480TB
After the supply of the slurry of N and glycol is completed,
Until carbonization is completed, CO_TwoContinued to supply. Reactor
5 minutes after the exhaust gas exceeds 5000 SCFH,
The carbonization was considered complete. The product is 248.9 ° C.
Vacuum strip with nitrogen at (480 ° F)
And filtered through Celite 535
Later, it had the following final properties: calcium (% by weight)
9.4; sulfur (% by weight) 2.9; glycol (% by weight)
0.6; carbonate C (% by weight) 1.8; TBN (m
gKOH / g) 272; PM flash point 18
2.2 ° C (360 ° F); Viscosity (cSt, 100 ° C) 1
06; BS & W (% by volume) <0.05. Preparation of the Batch Process of Example I and Example II
Reaction scheme for the preparation of the batch process of the invention described in I
Table I provides a comparison of cycle times. [0039] [Table 3]                                  Table I            Comparison of reaction cycle times of Example I and Example III     Process Example I Example III                                               (Minutes) 1. Dodecyl phenol in slurry     5W oil, glycol and 180     TBN Ca (OH)_TwoSupply 65 65 2. Supply sulfur 15 60 3. Reactor for sulfidation reaction     Heat to 165.6 ° C 120-180 0 4. Retention of reaction 60 30 5.5W in oil and glycol     Ca (OH)_Two480 TBN     Supply slurry 40 80 6. N_TwoStripping with 20 0 7. Carbon dioxide conversion until exhaust gas leakage 60 40 8. Repeat steps 5-7 120 0 Reaction cycle time (min) 500-560 275 Both preparations are essentially equivalent by treating the same amount of reactants
In the amount and quality of the product
The improvement of the present invention carried out in
Decreased by ~ 285 minutes. This significant decrease is new and
It is possible in a way that is not obvious,
Of the process of carbonization and carbonation by the batch method of the present invention.
You. In particular, the two stages required in the batch method of Example I
The carbonation of the floor is, in the present invention, 480 TBN
Ca (OH)_Two/ 5W oil slurry and glycol
CO2 conversion should be carried out at the same time as feeding to the reactor.
And be excluded by. This feature of the present invention
The problem of high viscosity in the reaction mixture (this problem
Requires two stages of carbonation as used in
At the same time as described in Example II
Excessive carbonation associated with a continuous process, such as
Or lack of carbon dioxide (the problem is phenate
(Which would cause water durability difficulties in the product). The product prepared in Example II (continuous process)
The water durability of the overbased phenate obtained was determined in Example III.
The overbased phenate produced according to the invention described
Compared to water durability. Two phenenes of normal processing level
Contains a major proportion of lubricating oil and a small effective amount of ash
Dispersant, low base calcium sulfonate, high base
Magnesium sulfonate, oxidation inhibitor and dialkyl
Standard commercial lubricating oil formulations containing zinc dithiophosphate
Was mixed in. Including the overbased phenate of Example II
The water durability of a standard formulation having the supersalt of Example III
Water Durability and Ratio of Standard Formulations Containing Base Phenates
70 ° F. or 54.4 ° C.
(130 ° F) and three different water levels in the formulation
(0.10, 0.15 and 0.20% by weight)
After storage for 6 weeks, clouding and settling in a sample of the formulation
The fall was measured. Thus, six separates of the standard formulation
Samples were tested for each overbased phenate. Water endurance
Sex test results are summarized in Table II below. [0041] [Table 4]                                 Table II          Water durability test of the phenates of Examples II and III               21.1 ℃ storage Storage at 54.4 ° C Water, weight% grade** Water, weight% grade 0.10 0.15 0.20 0.10 0.15 0.20 Example II A / tr * A / tr M / 15 Superior A / tr M / 15 M / 20 Boundary Example III A / tr A / tr A / tr Ideal A / tr A / tr M / 20 Excellent * Haze / settling; Haze grade is for best clarity
Start with "A" and grade "D" or higher
Considers to have failed. Settling is measured in volume% and
“Tr” means a slight amount of sedimentation. During six weeks of storage
Sedimentation> 1% at any time is rejected. ** Grades are assigned as follows:grade Standard No clouding or settling at any water level Excellent cloudiness or settling in 0.20% water Borderline cloudy or sediment rejected in 0.15% water Poor 0.10% water rejection of cloudiness or settling As demonstrated by the data set forth in Table II above, the present invention
The method of Example III (Example III) is similar to the continuous method of Example II.
Significantly improved overbased phenates produced
Yields an overbased phenate with improved water durability. The data set forth in Tables I and II
In conclusion, the method of the present invention significantly increases the throughput of the batch method.
At the same time as it is usually associated with batch production.
To achieve excellent water durability. The main features and embodiments of the present invention are as follows.
It is. 1. Process: a) into the reactor in a molar ratio of 0.1: 1 to 1.0: 1
From alkaline earth metal bases and alkylphenols
Providing a pre-heated mixture consisting essentially of
The product is charged to the reactor at 137.8-193.3C (280-38).
At a temperature in the range of 0 ° F .;
In a vessel, simultaneously, but separately, alkylphenol
0.1 to 1.0 mole of the solvent of the accelerator per mole of
Pay, then b) Raise the reaction temperature to 137.8-193.3 ° C (280-3
80 ° F) while maintaining the exotherm of the reaction and
20 to 180 at the speed to control the generation of exhaust gas
Over a period in the range of minutes, the alkyl
1.0-2.0 moles per mole of phenol
Supply sulfur, c) When the supply of sulfur is complete, 137.8-193.
At reaction temperatures in the range of 3 ° C (280-380 ° F)
To form sulfided alkaline earth metal alkyl phenates
Allow the contents in the reactor to interact for a time sufficient
Let d) Raise the reaction temperature to 137.8-193.3 ° C (280-3
80 ° F) while maintaining in the reactor
Reacting components react to form an overbased phenate
Controls that are not substantially larger or smaller than the speed
At a rolled feed rate, (i) the alkylphenol
0.5 to 2 moles of alkaline earth metal salt per mole
Group, (ii) 0.5 per mole of alkylphenol
~ 2.0 moles of accelerator solvent and (iii) alkali
0.40 to 0.95 mole per mole of base of earth metal
At the same time into the reactor.
Alkaline earth metal sulfide alkylene
Convert the salt to an overbased phenate, e) Reaction of alkaline earth metal base and promoter solvent.
When the supply to the vessel is completed, the supplied carbon dioxide
When it is no longer absorbed into the reaction medium, the reactor
Carbonization evidenced by a sharp increase in exhaust gas in the environment
Until the completion of the reaction, the supply of the carbon dioxide is continued, f) 204.4 to 248.9 ° C under vacuum (400 to 48
At a temperature in the range of 0 ° F.).
Solvents of knol and promoter are removed by purging with inert gas
And then g) filtering the resulting reaction product mixture and filtering
Recovering product from the lubricating oil formulation
Overbased sulfided alka with excellent water durability
A method for producing an earth metal alkyl phenate.
To carry out this method with a reaction cycle time of 6 hours or less.
And said filtered product is for at least 8 hours
Batch of a process having a cycle time of the reaction of
More specifically, it has water durability characteristics normally associated with manufacturing.
How to sign. 2. Alkaline earth metal base is calcium hydroxide
Dodecyl phenol, an alkyl phenol
And the solvent of the accelerator is ethylene glycol.
2. The method of claim 1, wherein the method comprises: 3. Calcium hydroxide in step (a)
/ Dodecylphenol molar ratio of 0.4-0.6: 1
Yes, ethylene glycol / dodeci in step (a)
And the molar ratio of phenol is 0.4 to 0.6: 1.
In step (b), the molar ratio of sulfur / dodecylphenol is
1.3 to 1.6: 1, the hydroxylation in step (d)
When the molar ratio of calcium / dodecylphenol is 1.0 to
1.5: 1, ethylene glycol in step (d)
Ole / dodecylphenol molar ratio of 1.0 to 1.5:
1 and supplied in steps (d) and (e)
CO_Two/ Dodecylphenol molar ratio is 1.0 ~
3. The method of claim 2 wherein the ratio is 1.5: 1. 4. In steps a), b), c) and d)
Reaction temperature of 148.9 to 182.2 ° C (300 to 3
2. The method of claim 1, wherein the temperature is maintained within a range of 60 ° F.
Law. 5. CO supplied in step d)_Two/
The base of the alkaline earth metal is 0.75 to 0.85: 1.
The method of claim 1, wherein 6. Alkaline earth metal base is calcium
Or magnesium oxide or hydroxide, above
2. The method according to item 1. 7. Converting the reaction of step c) to a low base alkali
Item 1. The above item 1 which is carried out in the presence of an earth metal sulfonate.
The described method. 8. The sulfonate is C₁₅-C₈₀Range
Alkylbenzenesulfonic acid having an alkyl substituent
Calcium and alkaline earth metal base
The method according to claim 7, which is a lucium base. 9. The reaction of steps c) and d) is
The method according to claim 1, which is carried out in the presence of a diluent. 10. Alkaline earth metal base is alkaline
Earth metal oxides or hydroxides,
Is ethylene glycol, and steps a), b), c) and
And the reaction temperature in d) is 148.9-182.2 ° C.
(300-360 ° F.)
Reaction in the presence of low base alkali metal sulfonate
And carrying out the reactions of steps c) and d)
Carried out in the presence of excipients and supplied in step d)
CO_Two/ The ratio of the oxide or hydroxide is 0.75
The method of claim 1 wherein the ratio is 0.85: 1. 11. Alkaline earth metal base is calcium
Base and the alkali metal sulfonate is a C₁₅
-C₈₀With alkyl substituents in the range
11. The method according to the above item 10, which is calcium sulfonate.
Law. 12. Calcium base is calcium hydroxide
And the alkyl substituent is C_Two-C_Fourmonomer
12. The method according to claim 11, which is derived from a polymer of
Law. 13. Alkylphenol is dodecylfe
12. The method of claim 11, which is knol. 14. Calcium hydroxide in step a)
/ Alkylphenol in a molar ratio of 0.4 to 0.6: 1
Yes, ethylene glycol / alkyl in step a)
The phenol molar ratio is 0.4-0.6: 1,
Ethylene glycol / alkylphenol in a)
Is from 0.4 to 0.6: 1, and in step b)
The molar ratio of sulfur / alkylphenol is 1.3-1.
6: 1 and calcium hydroxide / a in step d)
The molar ratio of the alkylphenol is 1.0 to 1.5: 1.
The ethylene glycol / alkyl phenol in step d)
The molar ratio of the enol is from 1.0 to 1.5: 1, and
CO supplied in steps d) and e)_TwoMolar ratio of
Wherein the ratio is 1.0 to 1.5: 1.
Law. 15. Alkylphenol is dodecylfe
15. The method according to claim 14, which is knol.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C10N 30:04 C10N 30:04 30:10 30:10 40:25 40:25 70:00 70:00 (56) References Table 3-505884 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 319/14 C07C 323/20 C10M 159/22 C10M 177/00 C10N 10:04 C10N 30:04 C10N 30:10 C10N 40:25-40:28 C10N 70:00

Claims (1)

(57) [Claim 1] Step: a) In a reactor, an alkali earth metal base and an alkyl phenol are essentially separated from each other in a molar ratio of 0.1: 1 to 1.0: 1. Is supplied to the reactor, where the mixture is charged to the reactor at 137.8-193.3C (280-38).
0 ° F.); into the reactor, simultaneously but separately, from 0.1 to 1.0 mole of promoter solvent per mole of alkylphenol; Next, b) the reaction temperature was increased to 137.8 to 193.3 ° C. (280 to 3
80 ° F), while maintaining the temperature within the range of 20 to 180 at a rate that controls the heat generation of the reaction and the generation of exhaust gas.
Minutes of molten sulfur per mole of alkylphenol are fed into the reactor over a time period in the range of minutes, c) when the sulfur feed is complete, 137.8 ~ 193.
Allowing the contents in the reactor to interact for a period of time sufficient to form a sulfurized alkaline earth metal alkyl phenate at a reaction temperature in the range of 3 ° C (280-380 ° F); d) reaction temperature 137.8-193.3 ° C (280-3
At a controlled feed rate that is not substantially greater or less than the rate at which the reactants present in the reactor react to form the overbased phenate, while maintaining the temperature within the range of 80 ° F. (I) 0.5-2 moles of alkaline earth metal base per mole of alkylphenol, (ii) 0.5 per mole of alkylphenol.
By simultaneously feeding .about.2.0 moles of a promoter solvent and (iii) 0.40 to 0.95 moles of carbon dioxide gas per mole of base of an alkaline earth metal into the reactor. E) converting the sulfurized alkaline earth metal alkyl phenate to an overbased phenate; e) when the supply of the alkaline earth metal base and promoter solvent to the reactor is complete, the supplied carbon dioxide is converted to a reaction medium. When it is no longer absorbed into the reactor, the carbon dioxide feed is continued until the completion of the carbonation reaction, as evidenced by a sharp increase in the exhaust gas in the reactor; f) 204.4-248. 9 ° C (400-48
At a temperature in the range of 0 ° F.), unreacted alkylphenol and promoter solvents are removed by purging with an inert gas, and g) the resulting reaction product mixture is filtered and the filtered product is recovered. A process for producing an overbased sulfurized alkaline earth metal alkyl phenate having excellent water durability properties in a lubricating oil formulation, the method being carried out with a reaction cycle time of 6 hours or less. Further comprising, and wherein the filtered product has water endurance characteristics normally associated with batch production of the product in a process having a cycle time of the reaction of at least 8 hours.