CN110591788A - Composition for inhibiting generation of ZDDP oil sludge and application thereof - Google Patents
Composition for inhibiting generation of ZDDP oil sludge and application thereof Download PDFInfo
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- CN110591788A CN110591788A CN201910845081.8A CN201910845081A CN110591788A CN 110591788 A CN110591788 A CN 110591788A CN 201910845081 A CN201910845081 A CN 201910845081A CN 110591788 A CN110591788 A CN 110591788A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/086—Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
A composition for inhibiting ZDDP sludge formation is provided, the composition comprises 12-29.86% by mass of an alkyl phenate and a derivative thereof; 11.6 to 23.89 percent of succinimide and derivatives thereof or succinate and derivatives thereof; 8.47 to 28.40 percent of alkyl diphenylamine and derivatives thereof; 40.96-59.88% of phenolic compound. The ZDDP is an important reason for generating oil sludge in the using process of hydraulic oil, and the composition provided by the invention can obviously reduce insoluble substances generated by the ZDDP decomposition, can further prevent the insoluble substances from agglomerating and depositing, and can reduce the generation amount of the oil sludge. In the actual use process, the generation amount of hydraulic oil sludge can be obviously improved, the blockage of hydraulic equipment pipelines and valves is avoided, the abrasion is reduced, and the composition has the advantages of simple preparation method and lower manufacturing cost.
Description
Technical Field
The invention relates to the technical field of lubricating oil, in particular to a composition for inhibiting ZDDP sludge generation and application thereof.
Background
The oil sludge is an important product of oil product oxidative deterioration, can bring serious influence to a hydraulic system, causes oil circuit and filter element blockage and friction pair abrasion, and simultaneously can also accelerate the deterioration of hydraulic oil. As hydraulic equipment develops towards miniaturization, high pressure, high speed, large flow and automation, the requirements on hydraulic components are more strict, the precision requirement is higher, the sensitivity of the device to impurities is increased, and the equipment is abraded and failed as long as tiny impurity particles exist, the particles are not only polluted by foreign particles, but also more importantly, oil sludge generated by oxidation and hydrolysis of hydraulic oil. The oil sludge in the hydraulic oil mainly comes from two sources, namely, an oxidation product generated by oxidation of base oil, wherein the oxidation reaction mainly occurs under the condition of metal ion catalysis; the second is the reaction product of ZDDP. The action forms of the ZDDP in producing oil sludge under different conditions are different, and the ZDDP acts as an oxidation inhibitor at 120 ℃ and then becomes zinc sulfate. When the temperature reaches above 140 ℃, the ZDDP undergoes a thermal decomposition reaction to generate insoluble polyphosphate. Under low temperature water conditions, ZDDP will deteriorate to produce zinc dialkylphosphate, which has a very low tendency to dissolve in oil and will form micellar structures. In the use process of hydraulic oil, water pollution is a very common phenomenon, so in the use environment of the hydraulic oil, no matter under a high-pressure heavy-load working condition or a medium-low pressure working condition, ZDDP can be decomposed and deteriorated in different degrees, insoluble substances insoluble in oil are generated, and finally, the ZDDP can be agglomerated to form oil sludge, so that oil circuits, filter cores and precise valves of a hydraulic system are blocked and equipment is abraded, so that the phenomena of insufficient oil supply, valve failure, crawling, damage to sliding shoes and gears and the like are caused, and serious threats are caused to production safety.
China has no strict requirement on the aspect of hydraulic oil sludge control, the thermal stability specifies that the content of the oil sludge is less than 100mg/100ml, and the foreign standard specifies that the content of the oil sludge is less than 25mg/100 ml. Although the oil sludge content of many domestic gray hydraulic oil products using the ZDDP additive meets the national standard, the oil sludge content far exceeds the foreign standard. In order to control cost, some enterprises use ZDDP with poor performance, which results in the oil sludge content not reaching the standard.
Disclosure of Invention
The present invention has been made in view of the above problems occurring in the prior art, and an object of the present invention is to provide a composition which can reduce sludge in hydraulic oil caused by ZDDP additives, ensure that pipelines and valves are not clogged, reduce wear, and ensure normal use of the hydraulic oil.
The technical scheme of the invention is that the composition for inhibiting the generation of the ZDDP oil sludge comprises the following components in percentage by mass:
alkyl phenates and derivatives thereof: 12 to 29.86 percent;
succinimide and its derivatives or succinate and its derivatives: 11.6 to 23.89 percent;
alkyl diphenylamines and their derivatives: 8.47 to 28.40 percent;
a phenolic compound: 40.96-59.88%.
The alkylphenol and the succinimide have extremely strong cleaning and dispersing effects, and can be quickly combined with oil sludge in the oil, so that the alkylphenol and the succinimide are well dissolved in the oil. The phenolic compound and the alkyl diphenylamine are chain terminators, can be rapidly combined with peroxy radicals ROO < - > so as to carry out terminal oxidation reaction, and can enlarge the range of oxidation inhibition temperature to be more than 100 ℃ by the synergy of the phenolic compound and the alkyl diphenylamine. The compounds act together, so that not only can the oxidation be restrained from the source, but also the oxidized products can be treated, and therefore, the compounds can act on the whole process of oil sludge generation to achieve the effect of restraining the oil sludge generation. Further, the alkylphenol salt and the derivative thereof are one or a mixture of two or more of sulfurized calcium alkyl phenolate, formaldehyde condensed calcium alkyl phenolate and calcium alkyl phenolate.
Further, the succinimide and the derivative thereof are one or a mixture of more than two of mono-succinimide, di-succinimide, poly-succinimide and boronized polyisobutenyl succinimide.
Further, the succinate and the derivative thereof are polyisobutylene succinate.
Further, the alkyl diphenylamine and the derivative thereof are one or a mixture of two or more of alkylated diphenylamine, styryl octyl diphenylamine, nonyl diphenylamine, N' -sec-butyl-p-phenylenediamine, and N-phenyl- α -naphthylamine.
Further, the above-mentioned phenol type compound is 2, 6-tert-butyl-p-cresol, 2, 4-dimethyl-6-tert-butylphenol, 4-thiobis (2-tert-butyl-6-methylphenol).
The invention also provides the application of the composition for inhibiting the generation of ZDDP sludge, which is applied to a lubricant containing ZDDP, and the application method comprises the following steps: the composition for suppressing the formation of ZDDP sludge, which accounts for 0.5% by mass of the ZDDP-containing lubricant, was added directly to the ZDDP-containing lubricant and stirred uniformly at 50-60 ℃.
The invention also provides a preparation method of the composition for inhibiting the generation of ZDDP oil sludge, which is characterized by mixing alkylphenol salts and derivatives thereof, succinimide and derivatives thereof or succinate and derivatives thereof, alkyl diphenylamine and derivatives thereof and phenolic compounds, heating to 75-90 ℃, stirring for 60-420 minutes, and filtering to obtain the ZDDP oil sludge.
The invention has the advantages that: the manufacturing method is simple and easy to operate, the manufactured product is low in price, and the content of oil sludge caused by ZDDP can be obviously reduced, so that pipelines and valves are prevented from being blocked, equipment is protected from being worn, and the service life of oil products is prolonged.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments in order to make the present invention better understood by those skilled in the art.
Example 1
Compositions 1, 2 and 3 were prepared in mass percent.
Composition 1
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: 13% of medium-alkali sulfurized calcium alkyl phenate; 18% of mono-succinimide; 15% of nonyl butyl diphenylamine; 54 percent of ditert-butyl-p-cresol.
Composition 2
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: medium base number sulfurized calcium alkyl phenate 18.3%; 18.4% of mono-succinimide; 17.1 percent of nonylbutyl diphenylamine; 46.2 percent of di-tert-butyl-p-cresol.
Composition 3
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: medium base number sulfurized calcium alkyl ester 21.6%; 20.7% of mono-succinimide; 20.3 percent of nonylbutyl diphenylamine; and 37.4 percent of di-tert-butyl-p-cresol.
Testing of the content of thermally Stable oil sludge
To compare the effect of compositions 1, 2, and 3 on the inhibition of thermally stable sludge formation, ZDDP was added to the base oil at 0.5% loading, and as a ZDDP control, compositions 1-3 and ZDDP formulated as described above were added to the base oil at 0.4% and 0.5% loading, respectively, and the thermally stable sludge content was tested.
The ZDDP is T204 and is purchased from synthetic chemical engineering;
the base oil is 40 million-two minus and 40 million-two minus, and is purchased from asphalt company Limited in North of Panjin;
blending two base oils of 40 million-two minus and 40 million-two minus of Beili according to the proportion of 64:36 to obtain the base oil of the composition and ZDDP.
The oil sludge content testing method is an SH/T0209 hydraulic oil thermal stability testing method;
the results of the sludge content tests for compositions 1, 2, 3 of example 1 in combination with ZDDP and ZDDP alone are shown in table 1.
Table 1 results of thermal stability test in example 1
Example 2
Compositions 1, 2 and 3 were prepared in mass percent.
Composition 1
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: 13% of high-base-number sulfurized calcium alkyl phenate; 18% of bis-succinimide; 15% of nonyl butyl diphenylamine; 54 percent of ditert-butyl-p-cresol.
Composition 2
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: high base number sulfurized calcium alkyl 18.3%; 18.4% of bis-succinimide; 17.1 percent of nonylbutyl diphenylamine; 46.2 percent of di-tert-butyl-p-cresol.
Composition 3
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: high base number sulfurized calcium alkyl 21.6%; 20.7% of bis-succinimide; 20.3 percent of nonylbutyl diphenylamine; and 37.4 percent of di-tert-butyl-p-cresol.
Testing of the content of thermally Stable oil sludge
To compare the effect of the compositions on the inhibition of thermally stable sludge formation, ZDDP was dosed at 0.5% to the base oil and as a ZDDP control, the thermally stable sludge content was tested by dosing each of compositions 1-3 and ZDDP from the above formulations at 0.4% and 0.5% respectively.
The ZDDP is F203, available from southern Petroleum additives, Inc. without tin;
the base oil is 40 million-two minus and 40 million-two minus, and is purchased from asphalt company Limited in North of Panjin;
blending two base oils of 40 million-two minus and 40 million-two minus of Beili according to the proportion of 64:36 to obtain the base oil of the composition and ZDDP.
The oil sludge content testing method is an SH/T0209 hydraulic oil thermal stability testing method;
the results of the sludge content tests for compositions 1, 2, 3 of example 2 in combination with ZDDP and ZDDP alone are shown in table 2.
Table 2 thermal stability test results in example 2
Example 3
Compositions 1, 2, 3 and 4 were prepared in mass percent.
Composition 1
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: medium base number sulfurized calcium alkyl 11.9%; 17.3% of mono-succinimide; 17.1 percent of nonylbutyl diphenylamine; 53.7 percent of ditert-butyl-p-cresol.
Composition 2
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: high base number sulfurized calcium alkyl 11.9%; 17.3 percent of bis-succinimide; 17.1 percent of nonylbutyl diphenylamine; 53.7 percent of ditert-butyl-p-cresol.
Composition 3
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: medium base number sulfurized calcium alkyl phenate 12.6%; 21.5% of polyisobutylene succinate; 18.4 percent of styryl octyl diphenylamine; 47.5 percent of ditert-butyl-p-cresol.
Composition 4
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: medium base number sulfurized calcium alkyl phenate 12.6%; 21.5% of bis-succinimide; 18.4 percent of styryl octyl diphenylamine; 47.5 percent of ditert-butyl-p-cresol.
Testing of the content of thermally Stable oil sludge
To compare the inhibitory effect of the compositions on the amount of thermally stable sludge formation, ZDDP was added to the base oil at a 0.5% loading as a ZDDP control; the above formulated compositions 1-4 and ZDDP were dosed at 0.4% and 0.5% respectively into base oil and tested for heat stable sludge content.
The ZDDP is KT2038, available from Jinzhou Coretai lubricating oil additives, Inc.;
the base oil is 40 million-two minus and 40 million-two minus, and is purchased from asphalt company Limited in North of Panjin;
blending two base oils of 40 million-two minus and 40 million-two minus of Beili according to the proportion of 64:36 to obtain the base oil of the composition and ZDDP.
The oil sludge content testing method is an SH/T0209 hydraulic oil thermal stability testing method;
the results of the sludge content tests for compositions 1, 2, 3 of example 3 in combination with ZDDP and ZDDP alone are shown in table 3.
Table 3 thermal stability test results in example 3
Example 4
Compositions 1, 2, 3 and 4 were prepared in mass percent.
Composition 1
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: 13.7 percent of high-base-number sulfurized calcium alkyl phenate; 14.3% of bis-succinimide; 19.7 percent of nonylbutyl diphenylamine; methylene 4, 4' -thiobis (2, 6-di-tert-butylphenol) 52.3%.
Composition 2
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: 13.7 percent of high-base-number sulfurized calcium alkyl phenate; 14.3% of bis-succinimide; 19.7 percent of nonylbutyl diphenylamine; 52.3 percent of di-tert-butyl-p-cresol.
Composition 3
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: medium base number sulfurized calcium alkyl 16.6%; 22.8% of polyisobutylene succinate; 23.5% of phenyl-alpha-naphthylamine; and 37.1 percent of di-tert-butyl-p-cresol.
Composition 4
A composition for inhibiting ZDDP sludge formation, comprising the following raw material components: medium base number sulfurized calcium alkyl 16.6%; 22.8% of polyisobutylene succinate; styryl octyl diphenylamine 23.5%; and 37.1 percent of di-tert-butyl-p-cresol.
Composition 5
To compare the inhibitory effect of the compositions on the amount of thermally stable sludge formation, ZDDP was added to the base oil at a 0.5% loading as a ZDDP control; the above formulated compositions 1-4 and ZDDP were dosed at 0.4% and 0.5% respectively into base oil and tested for heat stable sludge content.
The ZDDP is KT2038, available from Jinzhou Coretai lubricating oil additives, Inc.;
the base oil is 40 million-two minus and 40 million-two minus, and is purchased from asphalt company Limited in North of Panjin;
blending two base oils of 40 million-two minus and 40 million-two minus of Beili according to the proportion of 64:36 to obtain the base oil of the composition and ZDDP.
The oil sludge content testing method is an SH/T0209 hydraulic oil thermal stability testing method;
the results of the sludge content tests for compositions 1, 2, 3 of example 4 in combination with ZDDP and ZDDP alone are shown in table 4.
Table 4 thermal stability test results in example 4
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A composition for inhibiting ZDDP sludge formation, comprising in mass percent:
alkyl phenates and derivatives thereof: 12 to 29.86 percent;
succinimide and its derivatives or succinate and its derivatives: 11.6 to 23.89 percent;
alkyl diphenylamines and their derivatives: 8.47 to 28.40 percent;
a phenolic compound: 40.96-59.88%.
2. The composition for inhibiting ZDDP sludge formation of claim 1, wherein the alkyl phenate and its derivatives are one or a mixture of two or more of sulfurized calcium alkyl phenate, formaldehyde condensed calcium alkyl phenate, and calcium alkyl phenate.
3. The composition for inhibiting ZDDP sludge formation according to claim 1, wherein the succinimide and its derivatives are one or a mixture of two or more of mono-succinimide, di-succinimide, poly-succinimide, and boronated polyisobutenyl succinimide.
4. The composition for inhibiting ZDDP sludge formation according to claim 1, wherein the succinate ester and derivative thereof is a polyisobutylene succinate ester.
5. The composition for suppressing ZDDP sludge formation of claim 1, wherein the alkyldiphenylamine and derivatives thereof are one or a mixture of two or more of alkylated diphenylamine, styryl octyldiphenylamine, nonyldiphenylamine, N' -sec-butyl-p-phenylenediamine, and N-phenyl-alpha-naphthylamine.
6. The composition for inhibiting ZDDP sludge formation according to claim 1, wherein the phenolic compound is 2, 6-tert-butyl-p-cresol, 2, 4-dimethyl-6-tert-butylphenol, 4-thiobis (2-tert-butyl-6-methylphenol).
7. Use of a composition according to any of claims 1 to 6 for inhibiting ZDDP sludge formation in a lubricant containing ZDDP by: the composition for suppressing the formation of ZDDP sludge, which accounts for 0.5% by mass of the ZDDP-containing lubricant, was added directly to the ZDDP-containing lubricant and stirred uniformly at 50-60 ℃.
8. A process for preparing a composition for suppressing the formation of ZDDP oil sludge as claimed in any one of claims 1 to 6, wherein the composition is prepared by mixing an alkylphenate and its derivatives, a succinimide and its derivatives or a succinate and its derivatives, an alkyl diphenylamine and its derivatives, and a phenolic compound, heating to 75-90 deg.C, stirring for 60-420 min, and filtering.
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2019
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