CN104293449A - Composite calcium naphthenate-based lubricating grease and preparation method thereof - Google Patents
Composite calcium naphthenate-based lubricating grease and preparation method thereof Download PDFInfo
- Publication number
- CN104293449A CN104293449A CN201310300605.8A CN201310300605A CN104293449A CN 104293449 A CN104293449 A CN 104293449A CN 201310300605 A CN201310300605 A CN 201310300605A CN 104293449 A CN104293449 A CN 104293449A
- Authority
- CN
- China
- Prior art keywords
- acid
- lubricating grease
- calcium
- weight
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Lubricants (AREA)
Abstract
The invention discloses composite calcium naphthenate-based lubricating grease which is characterized by including following components, on the basis of the weight of the lubricating grease, 20-70 wt% of non-Newtonian calcium naphthenate, 1-10 wt% of a calcium salt of a higher fatty acid and 25-70 wt% of a basic oil. An infrared spectrogram of the non-Newtonian calcium naphthenate has a characteristic absorption peak of aragonite-type calcium carbonate. The invention also discloses a preparation method of the composite calcium naphthenate-based lubricating grease and the composite calcium naphthenate-based lubricating grease prepared through the same. The composite calcium naphthenate-based lubricating grease has excellent anti-corrosion property and anti-salt fog property, and has performances comprising a high-temperature-resistant performance, a water-resistant performance, an adhesive performance, a colloid stability and the like, which are better than those of composite calcium sulfonate-based lubricating grease. The composite calcium naphthenate-based lubricating grease has a longer lubricating service life. The preparation method is simple, environmental-protective, low in cost and stable in product quality.
Description
Technical field
The present invention relates to lubricating grease, particularly, relate to a kind of Composite calcium naphthenate base lubricating grease and preparation method thereof.
Background technology
Overbased calcium alkyl-salicylate has good detergent-dispersant performance, good acid neutralization capacity and excellent diffustivity, the purification agent of lubricating oil can be used as, be widely used in the additive of internal combustion (IC) engine lubricating oil, its technical development mainly makes its high alkalization, exactly calcium carbonate is distributed in thinning oil becomes a kind of colloidal dispersion system with having surface-active naphthenic acid calcium.Mostly overbased calcium alkyl-salicylate is the acidic components extracted from the distillate that crude distillation obtains, warp and Ca (OH)
2reaction, the contour alkalization technology of carbonating and obtain, about the Patents prepared has CN1465560 etc.
Utilize calcium sulfonate with high base number for raw material production lubricating grease, because it has excellent high temperature performance, mechanical stability, colloid stability, oxidation stability, water resisting property, non-corrosibility and antirust resistance to abrasion, since putting goods on the market, cause the extensive concern of domestic and international lubricating grease industry, but, although high base number composite calcium sulfonate base grease has very excellent over-all properties, but the high price of its raw materials for production calcium sulfonate with high base number and complicated preparation technology itself cause it not promoted rapidly, simultaneously, along with the requirement of people to environment protection is more and more higher, in calcium sulfonate with high base number production process must through sulfonation process the pollution of environment also received day by day to the concern of people.Find a kind of performance and the similar but large problem lubricating grease of the problems referred to above can being avoided to become people face at present of high base number composite calcium sulfonate base grease.
Summary of the invention
The object of this invention is to provide a kind of performance and high base number composite calcium sulfonate base grease is similar, cost is low, and preparation technology is simple, the lubricating grease of environmental protection and preparation method thereof.
The present inventor finds under study for action, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium naphthenate of 20-70 % by weight; The calcium salt of the higher fatty acid of 1-10 % by weight; The base oil of 25-70 % by weight, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the charateristic avsorption band of aragonite calcium carbonate, and described lubricating grease preferably also comprises the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 % by weight.Performance and the high base number composite calcium sulfonate base grease of this lubricating grease are similar, and cost is low, and preparation technology is simple, environmental protection.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of Composite calcium naphthenate base lubricating grease, it is characterized in that, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium naphthenate of 20-70 % by weight; The calcium salt of the higher fatty acid of 1-10 % by weight; The base oil of 25-70 % by weight, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the charateristic avsorption band of aragonite calcium carbonate.
Preferably, with lubricating grease weight for benchmark, described lubricating grease also comprises the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 % by weight.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium naphthenate of 30-55 % by weight; The calcium salt of the higher fatty acid of 2-6 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 2-10 % by weight; The base oil of 35-60 % by weight.
Second aspect, the invention provides Composite calcium naphthenate base preparation of greases method as above, it is characterized in that, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium naphthenate, higher fatty acid, the calcium salt of aromatic acid and/or small molecules mineral acid and/or lower fatty acid and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, add necessary additive, obtain finished product.
The third aspect, the invention provides a kind of Composite calcium naphthenate base preparation of greases method, it is characterized in that, the method comprises:
(1) by newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, aromatic acid and/or small molecules mineral acid and/or lower fatty acid reacts, heat up after reaction dehydration;
(3) step (2) reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
Fourth aspect, the invention provides the Composite calcium naphthenate base lubricating grease obtained by method as above.
Composite calcium naphthenate base lubricating grease of the present invention, not only the same with complex calcium sulfonate grease, there is excellent non-corrosibility and resistance to salt(spray)fog, but also there is the performance such as water resisting property and adhesivity, colloid stability, extreme pressure anti-wear being better than complex calcium sulfonate grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the infrared analysis spectrogram of the calcium carbonate in the overbased calcium alkyl-salicylate of embodiment 2.
Fig. 2 is the infrared analysis spectrogram of the calcium carbonate in the lubricating grease of embodiment 2 preparation.
Fig. 3 is the XRD crystal formation mensuration of the calcium carbonate in the lubricating grease of embodiment 2 preparation.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of Composite calcium naphthenate base lubricating grease, this lubricating grease have employed petroleum naphthenic acid calcium or synthesis calcium naphthenate is raw material, simultaneously containing composite calcium viscosifying agent.
Present invention also offers above-mentioned preparation of greases method.
On the one hand, the invention provides a kind of Composite calcium naphthenate base lubricating grease, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium naphthenate of 20-70 % by weight; The calcium salt of the higher fatty acid of 1-10 % by weight; The base oil of 25-70 % by weight, wherein, the infrared spectrum of non-newtonian fluid calcium naphthenate has the charateristic avsorption band of aragonite calcium carbonate.
Preferably, with lubricating grease weight for benchmark, lubricating grease also comprises the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 % by weight.
Preferably, with lubricating grease weight for benchmark, comprise following component: the non-newtonian fluid calcium naphthenate of 30-55 % by weight; The calcium salt of the higher fatty acid of 2-6 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 2-10 % by weight; The base oil of 35-60 % by weight.
The infrared absorption peak of the mainly carbonate that calcium carbonate occurs in infrared spectra, is divided into 4 regions: ν 1-1450cm
-1; ν 2-1080cm
-1; ν 3-870cm
-1with ν 4-710cm
-1.ν 1 bands of a spectrum are carbonate (CO
3 2-) antisymmetric stretching vibration absorption peak, ν 2 bands of a spectrum are carbonate symmetrical stretching vibration absorption peaks, and ν 3 bands of a spectrum are out-of-plane deformation vibration absorption peaks of carbonate, and ν 4 bands of a spectrum are in-plane bending vibration absorption peaks of carbonate.Generally speaking, the crystalline form of calcium carbonate can be distinguished by the difference of these absorption peaks.The characteristic absorbance of different crystal forms calcium carbonate is as follows: ν 3 bands of a spectrum of calcite type are 876cm
-1left and right, ν 4 bands of a spectrum are 712cm
-1left and right; ν 2 bands of a spectrum of aragonitic are 1082cm
-1left and right, ν 3 bands of a spectrum are 856cm
-1left and right, ν 4 bands of a spectrum are 712cm
-1and 700cm
-1(weak); Vaterite-type ν 3 bands of a spectrum are 876cm
-1left and right, ν 4 bands of a spectrum are 745cm
-1left and right; Amorphous ν 3 bands of a spectrum are 860cm
-1left and right.Environment residing for calcium carbonate is different, the peak position slightly difference of its infrared band.
Described non-newtonian fluid calcium naphthenate is at infrared spectrum 1082cm
-1left and right, 856cm
-1left and right, 712cm
-1left and right, 700cm
-1there is the charateristic avsorption band of aragonite calcium carbonate in place, total basicnumber is 250mgKOH/g-500mgKOH/g, preferred 300mgKOH/g-450mgKOH/g.Described non-newtonian fluid calcium naphthenate is obtained by transforming agent conversion by newton's body calcium naphthenate.And containing unformed calcium carbonate in newton's body calcium naphthenate, at infrared spectrum 1076cm
-1left and right, 860cm
-1there is unformed calcium carbonate charateristic avsorption band at left and right place.Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-500mgKOH/g, preferred 300mgKOH/g-450mgKOH/g, and after changing into non-newtonian fluid calcium naphthenate, its base number is constant.
In the present invention, higher fatty acid is carbon number is 8-20, the straight chain fatty acid of preferred 10-16 or hydroxy fatty acid, such as, at least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid, is preferably 12-oxystearic acid.
In the present invention, the molecular weight of small molecules mineral acid or lower fatty acid is less than or equal to 150.Wherein, small molecules mineral acid can be selected from least one in boric acid, phosphoric acid, sulfuric acid etc., is preferably boric acid and/or phosphoric acid; Lower fatty acid can be selected from least one in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid etc., is preferably acetic acid.
In the present invention, aromatic acid is the carboxylic acid having at least 1 carboxyl to be directly connected with aromatic ring, aromatic acid can be replace or unsubstituted aromatic acid, its substituting group can be at least one in alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno etc., and the molecular weight of aromatic acid is less than or equal to 550.Aromatic acid is preferably binary aromatic acid, such as, can be selected from least one in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.Be preferably phthalic acid, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, and at least one in methyl substituted biphenyl dicarboxylic acid, santowax dioctyl phthalate etc.
Described lubricant base can be mineral oil, synthetic oil, vegetables oil or their mixture, and 100 DEG C of kinematic viscosities are 4-150mm
2/ s, preferred 10-60mm
2/ s.Synthetic oil can be poly-a-olefin oil (PAO), Esters oil, alkyl-silicone oil, F-T synthesis wet goods.
Can also various additive be contained, as oxidation inhibitor, extreme pressure anti-wear additives, rust-preventive agent etc. in lubricating grease of the present invention.Wherein, the preferred arylamine kind antioxidant of oxidation inhibitor, accounts for the 0.01-5% of lubricating grease gross weight, preferred 0.1-2.5%, can be at least one in pentanoic, phenyl-a-naphthylamine and di-iso-octyldiphenylamine, preferred di-iso-octyldiphenylamine.Extreme pressure anti-wear additives accounts for the 0.5-12% of lubricating grease gross weight, preferred 0.8-8% can be at least one in dithio Acidic phosphates zinc, dithio dialkyl amido formic acid molybdenum, dithio dialkyl amido lead formiate, triphenylphosphorothionate, organic molybdenum complex compound, olefine sulfide, molybdenumdisulphide, tetrafluoroethylene, thiophosphoric acid molybdenum, clorafin, dibutyl dithiocaarbamate antimony, tungsten disulfide, Selenium Sulfide, fluorographite, calcium carbonate and zinc oxide; Rust-preventive agent accounts for the 0.01-4.5% of lubricating grease gross weight, preferred 0.1-2%, can be at least one in barium mahogany sulfonate, petroleum sodium sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid.
Second aspect, the invention provides Composite calcium naphthenate base preparation of greases method as above, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium naphthenate, higher fatty acid, the calcium salt of aromatic acid and/or small molecules mineral acid and/or lower fatty acid and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
In the present invention, for the calcium salt of the calcium salt of the calcium salt of non-newtonian fluid calcium naphthenate, higher fatty acid, aromatic acid, small molecules mineral acid and/or lower fatty acid and base oil described above, do not repeat them here.
It will be understood by those skilled in the art that the amount of part basis oil and the amount sum of surplus base oil are the total amount of base oil used, in the present invention, part basis oil is preferably 1:0.1-1 with the weight ratio of surplus base oil.
For non-newtonian fluid calcium naphthenate, can be obtained by transforming agent conversion by newton's body calcium naphthenate, such as, by newton's body calcium naphthenate, base oil Hybrid Heating to 50-80 DEG C, add required transforming agent and react, after all transforming agents add, be greater than 90 DEG C and be less than or equal to 110 DEG C, preferred 95-110 DEG C, constant temperature 40-100 minute, be then warming up to 150-170 DEG C of dehydration.
The third aspect, the invention provides a kind of Composite calcium naphthenate base preparation of greases method, comprising:
(1) by newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, aromatic acid and/or small molecules mineral acid and/or lower fatty acid reacts, heat up after reaction dehydration;
(3) step (2) products therefrom is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
In step (1), by newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent and react, after all transforming agents add, be greater than 90 DEG C and be less than or equal to 110 DEG C, preferred 95-110 DEG C, constant temperature 40-100 minute.
The weight ratio of newton's body calcium naphthenate and part basis oil is preferably 1:0.1-1.
Described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-500mgKOH/g, preferred 300mgKOH/g-450mgKOH/g.
Described transforming agent is selected from least one in water, fatty alcohol, aliphatic ether, lipid acid, naphthenic acid, alkanoic, aliphatic ketone, aliphatic amide, cycloalkanes amine, cycloalkanol, cycloalkanes ether, carbonic acid gas, aromatic alcohol, aromatic amine and alkyl benzene sulphonate (ABS), is preferably selected from least one in water, Virahol, methyl alcohol, ethanol, propyl alcohol, propyl carbinol, ketone, formaldehyde, glycol dimethyl ether, acetic acid, propionic acid, butyric acid, naphthenic acid, stearic acid, 12-oxystearic acid and Witco 1298 Soft Acid.Be more preferably A, B, C tri-class material, category-A material is ethanol, propyl alcohol, at least one in butanols and 12-oxystearic acid, category-B material is acetic acid, at least one in propionic acid and butyric acid, C class material is water, and feed postition is preferably category-A material to add prior to category-B material, namely first ethanol is added, propyl alcohol, at least one in butanols and 12-oxystearic acid, after mixing with newton's body calcium naphthenate, add acetic acid again, at least one in propionic acid and butyric acid, for the addition sequence of C class material water without particular requirement, can first add, can add later, also can add together with category-A material or category-B material.
The add-on of transforming agent is the 4-32% of newton's body calcium naphthenate weight, preferred 15-25%.When transforming agent is preferably A, B, C tri-class material, category-A material is at least one in ethanol, propyl alcohol, butanols and 12-oxystearic acid, category-B material is at least one in acetic acid, propionic acid and butyric acid, when C class material is water, the weight ratio of category-A material and category-B material and C class material is preferably 1:0.1-10:1-10, is more preferably 1:0.5-8:1-8.For the amount ratio between the concrete material selected in category-A material and category-B material and each material without particular requirement, as long as total amount can obtain better effect in above-mentioned scope.
In step (2), at 85-100 DEG C, add the suspension liquid of lime or calcium hydroxide, add higher fatty acid, stir 5-20 minute, add aromatic acid and/or small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 150-170 DEG C, preferably keep 30-60 minute to realize dehydration; Wherein, the addition sequence of higher fatty acid and aromatic acid and/or small molecules mineral acid and/or lower fatty acid can exchange.
In the present invention, higher fatty acid, aromatic acid, small molecules mineral acid, lower fatty acid as previously mentioned, do not repeat them here.
In the present invention, the H of higher fatty acid and aromatic acid and/or small molecules mineral acid and/or lower fatty acid
+total amount of substance and the OH contained by calcium hydroxide
-total amount of substance is equal, and the amount of calcium hydroxide also can excessive 1-10%.
In the present invention, in calcium hydroxide, the add-on of the suspension liquid of lime or calcium hydroxide is preferably the 1-15% of newton's body calcium naphthenate weight; With H
+amount of substance meter, the mol ratio of higher fatty acid and aromatic acid and/or small molecules mineral acid and/or lower fatty acid is preferably 1:1-10.
In the present invention, namely the suspension liquid of lime or calcium hydroxide refers to the suspension liquid that lime or calcium hydroxide are formed in water, and the solid content of suspension liquid is preferably 10-60 % by weight.
In step (3), be warmed up to 180-230 DEG C of constant temperature 5-20 minute; Be cooled to 150-160 DEG C, add surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
In the present invention, in step (1), part basis oil used is preferably 1:0.1-1 with the weight ratio of surplus base oil in step (3).
Fourth aspect, the Composite calcium naphthenate base lubricating grease that the preparation method that present invention also offers is provided by third aspect present invention obtains.
Compared with the Composite calcium naphthenate base lubricating grease obtained with the preparation method provided by second aspect, the Composite calcium naphthenate base lubricating grease that the preparation method that the third aspect provides obtains has better high thermal resistance, water resisting property and adhesivity, colloid stability and extreme pressure anti-wear.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following Examples and Comparative Examples:
Overbased or the overbased calcium alkyl-salicylate raw materials quality+transforming agent total mass of non-newtonian fluid calcium naphthenate %=()/lubricating grease total mass × 100%.Transforming agent all counts in the content of non-newtonian fluid calcium naphthenate.
In embodiment, overbased and overbased calcium alkyl-salicylate raw material, also can according to method preparation disclosed in CN101885677A from Xinjiang Land Fine Petrochemical Co., Ltd.
In comparative example, calcium sulfonate with high base number raw material is purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd..
Embodiment 1
The Composite calcium naphthenate base lubricating grease that the present embodiment is prepared for illustration of the present invention.
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total basicnumber is 320mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 80 DEG C, constant temperature 10 minutes; Add 1.8kg propyl carbinol, temperature controls at about 80 DEG C, stirs 10 minutes; Add 1.56kg butanic acid and 3.2kg water, stir 10 minutes; 95 DEG C of constant temperature 100 minutes, material retrogradation; Add the calcium hydroxide suspension liquid 10.8kg that solid content is 20 % by weight, stir 10 minutes, add the 12-oxystearic acid of 2.4kg, stir 10 minutes, add the terephthalic acid of 4.2kg, stir 10 minutes, under stirring, be warmed up to 160 DEG C, keep 45 minutes, dehydration; Be warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add HVI500SN lubricating base oil 15kg; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 38.8%; 12-oxystearic acid calcium 2.9%; Terephthalic acid calcium 6.0%; Lubricating base oil 52.3%.
Embodiment 2
The Composite calcium naphthenate base lubricating grease that the present embodiment is prepared for illustration of the present invention.
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add overbased calcium alkyl-salicylate that 33kg total basicnumber is 400mgKOH/g and 15kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 60 DEG C, constant temperature 10 minutes; Add 0.56kg ethanol, temperature controls at about 60 DEG C, stirs 10 minutes; Add 3.36kg propionic acid and 3.36kg water, stir 10 minutes; 100 DEG C of constant temperature 70 minutes, material retrogradation; Add the calcium hydroxide suspension liquid 5.2kg that solid content is 50 % by weight, stir 10 minutes, add the 12-oxystearic acid of 2kg, stir 10 minutes, add the boric acid of 2.6kg, stir 10 minutes, under stirring, be warmed up to 150 DEG C, keep 60 minutes, dehydration; Be warmed up to 180 DEG C of constant temperature 20 minutes.Then, be cooled to 150 DEG C, add HVI500SN lubricating base oil 10kg; Treat that temperature is cooled to 100 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 55.0%; 12-oxystearic acid calcium 3.2%; Lime borate 4.0%; Lubricating base oil 37.8%.
Embodiment 3
The Composite calcium naphthenate base lubricating grease that the present embodiment is prepared for illustration of the present invention.
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total basicnumber is 450mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 50 DEG C, constant temperature 10 minutes; Add 0.2kg n-propyl alcohol, 0.2kg propyl carbinol and 3.2kg water, temperature controls at about 50 DEG C, stirs 10 minutes; Add 2.96kg acetic acid, stir 10 minutes; 110 DEG C of constant temperature 40 minutes, material retrogradation; Cool to 85 DEG C, add the calcium hydroxide suspension liquid 7.8kg that solid content is 40 % by weight, stir 10 minutes, add the 12-oxystearic acid of 2kg, stir 10 minutes, add the phthalic acid of 3.5kg and the acetic acid of 2kg, stir 10 minutes, be warmed up to 170 DEG C under stirring, keep 30 minutes, dehydration; Be warmed up to 230 DEG C of constant temperature 5 minutes.Then, be cooled to 155 DEG C, add HVI500SN lubricating base oil 6kg; Treat that temperature is cooled to 120 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 42.5%; 12-oxystearic acid calcium 2.7%; Calcium phthalate 5.5%; Lime acetate 3.4%; Lubricating base oil 45.9%.
Embodiment 4
The Composite calcium naphthenate base lubricating grease that the present embodiment is prepared for illustration of the present invention.
A volume be 160L and with heating, stir, circulation, cooling normal-pressure reaction kettle in add naphthenate with superhigh base number calcium that 30kg total basicnumber is 320mgKOH/g and 30kg100 DEG C of kinematic viscosity is 31mm
2the HVI150BS lubricating base oil of/s, stirs, heats to 80 DEG C, constant temperature 10 minutes; Add 1.8kg propyl carbinol, temperature controls at about 80 DEG C, stirs 10 minutes; Add 1.56kg butanic acid and 3.2kg water, stir 10 minutes; 95 DEG C of constant temperature 100 minutes, material retrogradation.
Another volume be 50L and with heating, stir, circulation, cooling normal-pressure reaction kettle at 95 DEG C, add the calcium hydroxide suspension liquid 7.2kg that solid content is 30 % by weight, stir 10 minutes, add the 12-oxystearic acid of 2.4kg, stir 10 minutes, add the terephthalic acid of 4.2kg, stir 10 minutes, obtain 12-oxystearic acid calcium and terephthalic acid calcium.
The 12-oxystearic acid calcium of gained and terephthalic acid calcium are all squeezed in a upper still, stir, be warmed up to 160 DEG C under stirring, keep 45 minutes, dehydration, is finally warmed up to 200 DEG C of constant temperature 10 minutes.Then, be cooled to 160 DEG C, add HVI500SN lubricating base oil 15kg; Treat that temperature is cooled to 110 DEG C, circulating filtration, homogenizing, degassedly obtain finished product.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 38.8%; 12-oxystearic acid calcium 2.9%; Terephthalic acid calcium 6.0%; Lubricating base oil 52.3%.
Embodiment 5
The Composite calcium naphthenate base lubricating grease that the present embodiment is prepared for illustration of the present invention.
Composite calcium naphthenate base lubricating grease is prepared according to the method for embodiment 1, unlike, first add 1.56kg butanic acid, temperature controls at about 80 DEG C, stirs 10 minutes, then adds 1.8kg propyl carbinol and 3.2kg water, stirs 10 minutes.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 38.8%; 12-oxystearic acid calcium 2.9%; Terephthalic acid calcium 6.0%; Lubricating base oil 52.3%.
Embodiment 6
The Composite calcium naphthenate base lubricating grease that the present embodiment is prepared for illustration of the present invention.
Composite calcium naphthenate base lubricating grease is prepared according to the method for embodiment 1, unlike, 1.8kg propyl carbinol is replaced with 3.2kg ketone, 1.56kg butanic acid and 3.2kg water are replaced with 3.36kg naphthenic acid.Assay is in table 1.
In the lubricating grease that the present embodiment obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium naphthenate 38.8%; 12-oxystearic acid calcium 2.9%; Terephthalic acid calcium 6.0%; Lubricating base oil 52.3%.
Comparative example 1
Complex calcium sulfonate grease is prepared by the method for embodiment 1, unlike, overbased calcium alkyl-salicylate total basicnumber is that the calcium sulfonate with high base number of 320mgKOH/g replaces, and each performance data of lubricating grease finished product obtained is in table 1.
In the lubricating grease that this comparative example obtains, with lubricating grease weight for benchmark, consist of: non-newtonian fluid calcium sulphonate 38.8%; 12-oxystearic acid calcium 2.9%; Terephthalic acid calcium 6.0%; Lubricating base oil 52.3%.
Table 1 each lubricating grease properties of sample data
Each indication test method: dropping point: GB/T3498; Drawing cone in-degree: GB/T269; Corrosion: GB/T7326; Non-corrosibility: GB/T5018;
Water drenches number of dropouts: SH/T0109; Stencil oil-dividing: SH/T0324; Tetra-ball machine test: SH/T0202; Ball bearing lubricating life: ASTMD3336.
Embodiment 1 and comparative example 1 are compared and can find out, the water of Composite calcium naphthenate base lubricating grease of the present invention drenches number of dropouts much smaller than complex calcium sulfonate grease, Stencil oil-dividing value is much smaller than complex calcium sulfonate grease, tetra-ball machine test value is greater than complex calcium sulfonate grease, the bearing lubrication life-span is much larger than complex calcium sulfonate grease, water resisting property and the adhesivity of Composite calcium naphthenate base lubricating grease of the present invention are described, colloid stability, extreme pressure anti-wear, lubricating life is all better than complex calcium sulfonate grease, and Composite calcium naphthenate base lubricating grease of the present invention is the same with complex calcium sulfonate grease has the performances such as excellent non-corrosibility and resistance to salt(spray)fog.
Embodiment 1 and embodiment 4 are compared and can find out, Composite calcium naphthenate base lubricating grease prepared by original position, there is better water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, and there is longer lubricating life; Embodiment 1 and embodiment 5 are compared and can find out, in transforming agent, category-A material adds prior to category-B material, the Composite calcium naphthenate base lubricating grease of preparation, has better water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, and has longer lubricating life; Embodiment 1 and embodiment 6 are compared and can find out, transforming agent is A, B, C tri-class material, category-A material is at least one in ethanol, propyl alcohol, butanols and 12-oxystearic acid, category-B material is at least one in acetic acid, propionic acid and butyric acid, C class material is water, the Composite calcium naphthenate base lubricating grease of preparation, has better water resisting property and adhesivity, colloid stability and extreme pressure anti-wear, and has longer lubricating life.
As can be seen from Figure 1, the ν of the calcium carbonate in the overbased calcium alkyl-salicylate of embodiment 2
2bands of a spectrum are at 1076-1077cm
-1left and right, ν
3bands of a spectrum are 860cm
-1left and right.Be illustrated as amorphous calcium carbonate.
As can be seen from Figure 2, containing 1082cm in the infrared spectrum of the calcium carbonate in the lubricating grease prepared of embodiment 2
-1left and right, 855cm
-1left and right, 700cm
-1left and right, 713cm
-1the absorption peaks such as left and right are the charateristic avsorption band of aragonite calcium carbonate, illustrate that the amorphous calcium carbonate in overbased calcium alkyl-salicylate transforms in order to aragonite calcium carbonate.
As can be seen from Figure 3, the XRD crystal formation of the calcium carbonate in lubricating grease prepared by embodiment 2 measures, intensity peak is had near angle 26 °, 27 °, 46 °, 33.5 °, 36 °, 38 °, 43 °, consistent with aragonite standard spectrogram, illustrate to there is aragonite calcium carbonate in sample after transforming.
Composite calcium naphthenate base lubricating grease of the present invention, not only the same with complex calcium sulfonate grease, there is excellent non-corrosibility and resistance to salt(spray)fog, but also there is the performance such as water resisting property and adhesivity, colloid stability, extreme pressure anti-wear being better than complex calcium sulfonate grease, there is longer lubricating life.Preparation of greases technique of the present invention is simple, environmental protection, and cost is low, constant product quality.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (20)
1. a Composite calcium naphthenate base lubricating grease, is characterized in that, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium naphthenate of 20-70 % by weight; The calcium salt of the higher fatty acid of 1-10 % by weight; The base oil of 25-70 % by weight, wherein, the infrared spectrum of described non-newtonian fluid calcium naphthenate has the charateristic avsorption band of aragonite calcium carbonate.
2. lubricating grease according to claim 1, wherein, with lubricating grease weight for benchmark, described lubricating grease also comprises the small molecules mineral acid of 1-15 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 1-15 % by weight.
3. lubricating grease according to claim 2, wherein, with lubricating grease weight for benchmark, comprises following component: the non-newtonian fluid calcium naphthenate of 30-55 % by weight; The calcium salt of the higher fatty acid of 2-6 % by weight; The small molecules mineral acid of 2-10 % by weight and/or the calcium salt of lower fatty acid, and/or the calcium salt of the aromatic acid of 2-10 % by weight; The base oil of 35-60 % by weight.
4. according to the lubricating grease in claim 1-3 described in any one, wherein, described non-newtonian fluid calcium naphthenate is transformed by newton's body calcium naphthenate and obtains, and its total basicnumber is 250-500mgKOH/g.
5. according to the lubricating grease in claim 1-3 described in any one, wherein, straight chain fatty acid or the hydroxy fatty acid of described higher fatty acid to be carbon number be 8-20.
6. lubricating grease according to claim 5, wherein, described higher fatty acid is selected from least one in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.
7. the lubricating grease according to Claims 2 or 3, wherein, the molecular weight of small molecules mineral acid or lower fatty acid is less than or equal to 150.
8. lubricating grease according to claim 7, wherein, described small molecules mineral acid is selected from least one in boric acid, phosphoric acid, sulfuric acid, and described lower fatty acid is selected from least one in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.
9. the lubricating grease according to Claims 2 or 3, wherein, described aromatic acid is that replace or unsubstituted aromatic acid, and substituting group is at least one in the alkyl or aryl of alkyl, thiazolinyl, alkynyl, aryl, halo or perhalogeno, and the molecular weight of described aromatic acid is less than or equal to 550.
10. according to lubricating grease according to claim 9, wherein, described aromatic acid is selected from least one in phthalic acid that unsubstituted or C1-C5 alkyl replaces, m-phthalic acid, terephthalic acid, biphenyl dicarboxylic acid, santowax dioctyl phthalate.
Composite calcium naphthenate base preparation of greases method in 11. claim 1-10 described in any one, it is characterized in that, the method comprises: the calcium salt of the calcium salt of non-newtonian fluid calcium naphthenate, higher fatty acid, the calcium salt of aromatic acid and/or small molecules mineral acid and/or lower fatty acid and part basis oil are mixed, 180-230 DEG C of constant temperature refining, cooling, add surplus base oil, add necessary additive, obtain finished product.
12. 1 kinds of Composite calcium naphthenate base preparation of greases methods, it is characterized in that, the method comprises:
(1) by newton's body calcium naphthenate and part basis oil Hybrid Heating, add transforming agent, heat up and treat material retrogradation;
(2) in step (1) products therefrom, add lime or calcium hydroxide, add higher fatty acid, aromatic acid and/or small molecules mineral acid and/or lower fatty acid reacts, heat up after reaction dehydration;
(3) step (2) reaction gained mixture is warmed up to 180-230 DEG C of constant temperature refining, cooling, adds surplus base oil, adds necessary additive, obtains finished product.
13. preparation methods according to claim 12, wherein, in step (1), by newton's body calcium naphthenate, part basis oil Hybrid Heating to 50-80 DEG C, add required transforming agent to react, after all transforming agents add, be greater than 90 DEG C and be less than or equal to 110 DEG C of constant temperature 40-100 minute.
14. preparation methods according to claim 12, wherein, in step (2), at 85-100 DEG C, add the suspension liquid of lime or calcium hydroxide, add higher fatty acid, stir 5-20 minute, add aromatic acid and/or small molecules mineral acid and/or lower fatty acid, stir 5-20 minute, be warming up to 150-170 DEG C of dehydration.
15. preparation methods according to claim 12, wherein, in step (3), are warmed up to 180-230 DEG C of constant temperature 5-20 minute; Be cooled to 150-160 DEG C, add surplus base oil, treat that temperature is cooled to 100-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.
16. preparation methods according to claim 12, wherein, described newton's body calcium naphthenate is petroleum naphthenic acid calcium and/or synthesis calcium naphthenate, and its total basicnumber is 250-500mgKOH/g.
17. preparation methods according to claim 12, wherein, described transforming agent is selected from least one in water, fatty alcohol, aliphatic ether, lipid acid, naphthenic acid, alkanoic, aliphatic ketone, aliphatic amide, cycloalkanes amine, cycloalkanol, cycloalkanes ether, carbonic acid gas, aromatic alcohol, aromatic amine and alkyl benzene sulphonate (ABS), and the add-on of transforming agent is the 4-32% of newton's body calcium naphthenate weight.
18. preparation methods according to claim 17, wherein, described transforming agent is A, B, C tri-class material, category-A material is at least one in ethanol, propyl alcohol, butanols and 12-oxystearic acid, category-B material is at least one in acetic acid, propionic acid and butyric acid, C class material is water, and the add-on of transforming agent is the 15-25% of newton's body calcium naphthenate weight.
19. preparation methods according to claim 18, wherein, category-A material adds prior to category-B material.
The 20. Composite calcium naphthenate base lubricating grease obtained by the method in claim 12-19 described in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310300605.8A CN104293449B (en) | 2013-07-17 | 2013-07-17 | A kind of Composite calcium naphthenate base grease and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310300605.8A CN104293449B (en) | 2013-07-17 | 2013-07-17 | A kind of Composite calcium naphthenate base grease and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104293449A true CN104293449A (en) | 2015-01-21 |
| CN104293449B CN104293449B (en) | 2016-08-10 |
Family
ID=52313409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310300605.8A Active CN104293449B (en) | 2013-07-17 | 2013-07-17 | A kind of Composite calcium naphthenate base grease and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104293449B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113366096A (en) * | 2018-12-24 | 2021-09-07 | 卡乔有限责任公司 | Mineral oil-free lubricant and method of making a mineral oil-free lubricant |
| CN114806688A (en) * | 2022-04-25 | 2022-07-29 | 宝鸡文理学院 | Composite calcium sulfonate-based lubricating grease for industrial robot and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885677A (en) * | 2009-05-14 | 2010-11-17 | 中国石油化工股份有限公司 | Preparation method for high-alkaline calcium naphthenate |
| CN103627496A (en) * | 2012-08-28 | 2014-03-12 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based lubricating grease and preparation method therefor |
-
2013
- 2013-07-17 CN CN201310300605.8A patent/CN104293449B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885677A (en) * | 2009-05-14 | 2010-11-17 | 中国石油化工股份有限公司 | Preparation method for high-alkaline calcium naphthenate |
| CN103627496A (en) * | 2012-08-28 | 2014-03-12 | 中国石油化工股份有限公司 | Composite calcium naphthenate-based lubricating grease and preparation method therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113366096A (en) * | 2018-12-24 | 2021-09-07 | 卡乔有限责任公司 | Mineral oil-free lubricant and method of making a mineral oil-free lubricant |
| CN113366096B (en) * | 2018-12-24 | 2023-03-17 | 卡乔有限责任公司 | Mineral oil-free lubricant and method of making a mineral oil-free lubricant |
| CN114806688A (en) * | 2022-04-25 | 2022-07-29 | 宝鸡文理学院 | Composite calcium sulfonate-based lubricating grease for industrial robot and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104293449B (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103627496B (en) | A kind of Composite calcium naphthenate base lubricating grease and preparation method thereof | |
| CN104293449A (en) | Composite calcium naphthenate-based lubricating grease and preparation method thereof | |
| CN104449959A (en) | High-base number composite calcium-based grease and preparation method thereof | |
| CN104450111A (en) | Composite calcium sulfonate-calcium naphthenate-based grease and preparation method thereof | |
| CN104293452A (en) | Composite calcium naphthenate-based polyurea lubricating grease and preparation method thereof | |
| CN104560276A (en) | Compound calcium sulfonate-calcium naphthenate zirconium-based lubricating grease and preparation method thereof | |
| CN104212535B (en) | A kind of calcium naphthenate base octa-polyurea lubricating grease and preparation method thereof | |
| CN106032487B (en) | Lubricant composition and preparation method thereof | |
| CN103695137B (en) | A kind of Composite calcium naphthenate base lubricating grease and preparation method thereof | |
| CN104212611B (en) | A kind of Calcium naphthenate base polyurea grease and preparation method thereof | |
| CN104293450A (en) | Composite calcium naphthenate-based tetra-polyurea lubricating grease and preparation method thereof | |
| CN104293416A (en) | Composite calcium naphthenate-based hexa-polyurea lubricating grease and preparation method thereof | |
| CN104293451A (en) | Composite calcium naphthenate-based octa-polyurea lubricating grease and preparation method thereof | |
| CN104560277B (en) | A kind of calcium naphthenate zirconium base lubricating grease and preparation method thereof | |
| CN104212612B (en) | A kind of Calcium naphthenate base six polyurea grease and preparation method thereof | |
| CN104212610B (en) | A kind of calcium naphthenate-based tetrapolyurea lubricating grease and preparation method thereof | |
| CN106032479B (en) | Lubricant composition and preparation method thereof | |
| CN104449956A (en) | High base number composite calcium-based polyurea lubricating grease and preparation method thereof | |
| CN104560317A (en) | Compound calcium sulfonate-calcium naphthenate zirconium-based polyurea lubricating grease and preparation method thereof | |
| CN104560278A (en) | Calcium sulfonate-calcium naphthenate zirconium-based lubricating grease and preparation method thereof | |
| CN104560268A (en) | Compound calcium naphthenate zirconium-based lubricating grease and preparation method thereof | |
| CN104449957A (en) | Composite calcium sulfonate-calcium naphthenate-based urea hexamer grease and preparation method thereof | |
| CN104450114A (en) | Composite calcium sulfonate-calcium naphthenate-based urea tetramer grease and preparation method thereof | |
| CN104560325A (en) | Compound calcium naphthenate zirconium-based hexurea lubricating grease and preparation method thereof | |
| CN104449958A (en) | Composite calcium sulfonate-calcium naphthenate-based urea octamer grease and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |