CN1087027C - Process for preparing composite Li-Ca based grease - Google Patents
Process for preparing composite Li-Ca based grease Download PDFInfo
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- CN1087027C CN1087027C CN99107941A CN99107941A CN1087027C CN 1087027 C CN1087027 C CN 1087027C CN 99107941 A CN99107941 A CN 99107941A CN 99107941 A CN99107941 A CN 99107941A CN 1087027 C CN1087027 C CN 1087027C
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Abstract
The present invention relates to a method for preparing composite Li-Ca base lubricating grease. Fatty acid selected from C12C24 or at least one kind of monoacid in hydroxy fatty acid, water and base oil are mixed, heated and dissolved, calcium hydroxide, lithium hydroxide and at least one of dibasic acid selected from terephthalic acid or C2 to C12 fat dibasic acid are added a container is closed, the ingredients react under the conditions of 100 DEG C to 170 DEG C and 0.1Mpa to 0.6Mpa for 0.5 to 5.0 hours, and after the pressure is relieved, the ingredients are heated up and dewatered; surplus base oil is added for circular cooling, homogenization and degassing. The method has the advantages of simple operation and good repetitiveness; the prepared lubricating grease both has the performance of ordinary composite Li-Ca base lubricating grease, and has the advantages of high dropping point, good shear stability and bright external appearance.
Description
The invention belongs to the preparation method of lubricant, specifically a kind of preparation method of Li-Ca based grease.
In recent years, along with developing of automobile industry, the high performance of automobile and the prolongation of guarantee period were harsh more to the requirement of auto lubrication fat, required lubricating grease to have better high-temperature behavior and mechanical stability energy.
CN85108442A discloses " binary metallic based grease composition and preparation method thereof ", be to adopt " two step method " preparation complex lithium-calcium base grease, promptly earlier lipid acid or hydroxy fatty acid are mixed with Dormant oils, calcium oxide, lithium hydroxide, carry out the first step saponification, under about 130 ℃, the mixing acid that adds terephthalic acid or terephthalic acid and binary acid carries out the second step saponification.This preparation method's complex process, and wayward.
US5,350,531 disclose a kind of preparation of greases method, are that bright stock is mixed with the 12-oxystearic acid, 77～93 ℃ of reactions at least 30 minutes, add calcium hydroxide and lithium hydroxide then, carry out saponification reaction under 182～232 ℃.This method obtains 12-hydroxy lithium stearate-calcium fat mechanical stability preferably, and 100,000 times are cut off difference is 25, but dropping point is less than 200 ℃.
The object of the present invention is to provide the different method for preparing composite Li-Ca based grease of a kind of and above-mentioned patent, the composite Li-Ca lubricating grease that this method makes has the outward appearance of high dropping point, good shear stability and light.
Preparation method of the present invention comprises the following steps: being selected from C
12～C
24Lipid acid or at least a monoprotic acid in the hydroxy fatty acid, water and base oil mix and heating for dissolving, add calcium hydroxide, lithium hydroxide and be selected from terephthalic acid or C
2～C
12At least a diprotic acid in the binary acid, encloses container, at 100 ℃～170 ℃, 0.1MPa～0.6MPa reacted 0.5～5.0 hour down, and the dehydration that heats up after the release adds the circulation of surplus base oil and cools off, and homogenizing, the degassing get final product.Wherein the mol ratio of monoprotic acid and diprotic acid is 1: 0.1～0.8, and the add-on of calcium hydroxide is 5～50% of a monoprotic acid mole number, and the viscosifying agent consumption that acid-base reaction generates is 3～30% of a lubricating grease weight.
Specifically, preparation of greases method provided by the invention can be carried out in the following manner: monoprotic acid, water and part base oil mix, and be heated to 70～85 ℃ and make monoprotic acid dissolving, add calcium hydroxide, lithium hydroxide and diprotic acid, wherein the three can add simultaneously, also can add calcium hydroxide earlier, makes part monoprotic acid at first generate calcium soap with calcium hydroxide reaction, reacted about 5～20 minutes, and added diprotic acid and lithium hydroxide again.Encloses container is warming up to 100～170 ℃ then, preferred 110～160 ℃, keep reaction pressure 0.1～0.6MPa, preferred 0.1～0.5MPa, the reaction times is 0.5～5.0, preferred 0.6～3.0 hour, release, continue to be warming up to 205～215 ℃, add surplus base oil circulation cooling, add additive as required, carry out the homogenizing processing and the degassing at last, obtain all lubricating grease of even light.
Wherein the mol ratio of monoprotic acid and diprotic acid is 1: 0.1～0.8, preferred 1: 0.25～0.5.Bronsted lowry acids and bases bronsted lowry equivalent reaction, the add-on of calcium hydroxide is 5～50% of a monoprotic acid mole number, and is preferred 5～30%, surplus is a lithium hydroxide.Viscosifying agent is in the bronsted lowry acids and bases bronsted lowry and the salt of dehydration back generation, and the amount of viscosifying agent is 3～30% of a lubricating grease weight, preferred 5～25%.The effect of water is dissolving alkali and forms pressure in the closed reactor that therefore according to those skilled in the art's experience, the consumption of water can be 3～5 times of alkali gross weight.Base oil adds at twice, and this also is those skilled in the art's a general knowledge, in general, adds 1/2～3/4 of gross weight in the reactant earlier, adds the residue base oil after having reacted again to cool off.
Said monoprotic acid is to be selected from C
12～C
24, preferred C
16～C
20At least a acid in lipid acid or the hydroxy fatty acid, more preferably 12-oxystearic acid or stearic acid.Said diprotic acid is to be selected from terephthalic acid or C
2～C
12, preferred C
4～C
12Binary acid at least a acid, more preferably terephthalic acid, adipic acid, nonane diacid or sebacic acid.
Said base oil can be that 100 ℃ of viscosity are the Dormant oils and the ucon oil various commonly used of 3～50 centistokes, as 500SN oil petroleum refined by naphthenic, synthetic hydrocarbon oil, polyethers and ester class wet goods.
Lubricating grease of the present invention, to various additives commonly used, as oxidation inhibitor (di-iso-octyldiphenylamine and phenyl αNai An etc.), extreme pressure agent, rust-preventive agent etc. has excellent adaptability.Therefore, as required, this lubricating grease can also add various types of additives.
The preparation method of complex lithium-calcium base grease provided by the invention is simple to operate, good reproducibility, prepared lubricating grease is except that the performance that possesses common complex lithium-calcium base grease, the outward appearance that also has higher dropping point, good shear stability and light, for example, adopt the grease dropping point of the inventive method preparation can reach 305～330 ℃, cut off cone penetration and Drawing cone in-degree difference for 100,000 times less than 22.This lubricating grease can be used for the lubricated of automobile hub bearing.
The invention will be further described below by embodiment.
Embodiment 1
With 945 gram (3.15mol) ten dihydroxystearic acids, 5.9kg oil petroleum refined by naphthenic (100 ℃ of viscosity are 11 centistokes), the required whole water 925ml water of reaction, join in the autoclave pressure of 20 liters, heat temperature raising to 75 ℃, add 12.5g (0.17mol) calcium hydroxide, about 10 minutes of stirring reaction, make part 12-oxystearic acid at first generate the calcium soap of ten dihydroxystearic acids, add 231.3g (5.51mol) lithium hydroxide (LiOHH then with calcium hydroxide reaction
2O) and 255g (1.26mol) sebacic acid, airtight, at 145 ℃, 0.3MPa reaction 45 minutes down, venting is warming up to 210 ℃, adds Dormant oils 2.9kg, and cooling is sheared, and adds the 50g di-iso-octyldiphenylamine, the degassing.Obtain 320 ℃ of product dropping points, the difference of cutting off cone penetration and Drawing cone in-degree (promptly cutting off for 60 times) for 100,000 times is 7.Reaction conditions sees Table 1, and physicochemical property sees Table 2.
Embodiment 2
With 1027g (3.42mol) ten dihydroxystearic acids, 5.9kg oil petroleum refined by naphthenic (100 ℃ of viscosity are 14 centistokes), required whole water 638.6 water of reaction, join in the autoclave pressure of 20 liters, heat temperature raising to 75 ℃, add 50.3g (0.68mol) calcium hydroxide, about 10 minutes of stirring reaction, make part 12-oxystearic acid at first generate the calcium soap of ten dihydroxystearic acids, add 159.2g (3.79mol) lithium hydroxide (LiOHH then with calcium hydroxide reaction
2O) and 173g (0.87mol) sebacic acid, airtight, at 135 ℃, 0.2MPa reaction 1.5 hours down, venting is warming up to 210 ℃, adds Dormant oils 2.9kg, and cooling is sheared, and adds the 50g di-iso-octyldiphenylamine, the degassing.Obtain 305 ℃ of product dropping points, the difference of cutting off cone penetration and Drawing cone in-degree for 100,000 times is 12.Reaction conditions sees Table 1, and physicochemical property sees Table 2.
Embodiment 3
With 898g (2.99mol) ten dihydroxystearic acids, 5.9kg oil petroleum refined by naphthenic (100 ℃ of viscosity are 12 centistokes), required whole water 912.6 water of reaction, join in the autoclave pressure of 20 liters, heat temperature raising to 80 ℃, add 22.2g (0.30mol) calcium hydroxide, about 15 minutes of stirring reaction, make part 12-oxystearic acid at first generate the calcium soap of ten dihydroxystearic acids, add 228g (5.43mol) lithium hydroxide (LiOHH then with calcium hydroxide reaction
2O) and 286g (1.52mol) nonane diacid, airtight, at 115 ℃, 0.1MPa reaction 1 hour down, venting is warming up to 210 ℃, adds Dormant oils 2.9kg, and cooling is sheared, and adds the 50g di-iso-octyldiphenylamine, the degassing.Obtain 317 ℃ of product dropping points, the difference of cutting off cone penetration and Drawing cone in-degree for 100,000 times is 22.Reaction conditions sees Table 1, and physicochemical property sees Table 2.
Embodiment 4
With 945g (3.15mol) stearic acid, 5.9kg synthetic hydrocarbon oil (100 ℃ of viscosity are 15 centistokes), the required whole water 897.1ml of reaction, join in the autoclave pressure of 20 liters, heat temperature raising to 80 ℃, add 12.6g (0.17mol) calcium hydroxide, about 15 minutes of stirring reaction, make part 12-oxystearic acid at first generate the calcium soap of ten dihydroxystearic acids, add 244.3g (5.34mol) lithium hydroxide (LiOHH then with calcium hydroxide reaction
2O) and 182.5g (1.25mol) adipic acid, airtight, at 160 ℃, 0.5MPa reaction 1.0 hours down, venting is warming up to 210 ℃, adds Dormant oils 2.9kg, and cooling is sheared, and adds the 50g di-iso-octyldiphenylamine, the degassing.Obtain 330 ℃ of product dropping points, the difference of cutting off cone penetration and Drawing cone in-degree for 100,000 times is 18.Reaction conditions sees Table 1, and physicochemical property sees Table 2.
Embodiment 5
With 1254g (4.18mol) ten dihydroxystearic acids, 5.9kg oil petroleum refined by naphthenic (100 ℃ of viscosity are 32 centistokes), the required whole water 1192.8ml of reaction, join in the autoclave pressure of 20 liters, heat temperature raising to 80 ℃, add 31.8g (0.63mol) calcium hydroxide, about 15 minutes of stirring reaction, make part of stearic acid at first generate stearic calcium soap, add 298.2g (7.10mol) lithium hydroxide (LiOHH then with calcium hydroxide reaction
2O) and 346.9g (2.09mol) terephthalic acid, airtight, at 150 ℃, 0.4MPa reaction 1.5 hours down, venting is warming up to 210 ℃, adds Dormant oils 2.9kg, and cooling is sheared, and adds the 50g di-iso-octyldiphenylamine, the degassing.Obtain 320 ℃ of product dropping points, the difference of cutting off cone penetration and Drawing cone in-degree for 100,000 times is 16.Reaction conditions sees Table 1, and physicochemical property sees Table 2.
Table 1
| Example | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Monoprotic acid: diprotic acid (mol ratio) | 1∶0.4 | 1∶0.25 | l∶0.5 | 1∶0.4 | 1∶0.5 |
| Calcium hydroxide, mol% (monoprotic acid) | 10 | 40 | 20 | 10 | 30 |
| (ten dihydroxyl) stearic acid, mol | 3.15 | 3.42 | 2.99 | 3.15 | 4.18 |
| Terephthalic acid, mol | 2.09 | ||||
| Sebacic acid, mol | 1.26 | 0.87 | |||
| Nonane diacid, mol | 1.52 | ||||
| Hexanodioic acid, mol | 1.25 | ||||
| Lithium hydroxide, mol | 5.51 | 3.79 | 5.43 | 5.34 | 7.10 |
| Calcium hydroxide, mol | 0.17 | 0.68 | 0.30 | 0.17 | 0.63 |
| Di-iso-octyldiphenylamine, % | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Temperature of reaction, ℃ | 145 | 135 | 115 | 160 | 150 |
| Reaction pressure, MPa | 0.3 | 0.2 | 0.1 | 0.5 | 0.4 |
| Saponification time, h | 0.75 | 1.5 | 2.5 | 1.0 | 1.5 |
Table 2
* comparative example 1 is the 12-hydroxy lithium stearate of preparation according to a conventional method and the compositing lithio ester of sebacic acid.
| Analysis project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 * |
| Dropping point, ℃ | 320 | 305 | 317 | 330 | 320 | 273 |
| Cone penetration, 60 times 100,000 times differences of 0.1mm | 325 332 7 | 274 286 12 | 256 278 22 | 307 325 18 | 327 343 16 | 267 316 49 |
| Stencil oil-dividing (100 ℃, 30h), % | 2.55 | 2.94 | 2.34 | 3.44 | 4.21 | 3.25 |
| Corrosion (100 ℃, 24h) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
As can be seen from Table 2, adopt the complex lithium-calcium fat of method preparation provided by the invention to have high dropping point and good shear stability.
Claims (10)
1. the preparation method of a composite Li-Ca based grease is characterized in that, being selected from C
12～C
24Lipid acid or at least a monoprotic acid in the hydroxy fatty acid, water and base oil mix and heating for dissolving, add calcium hydroxide, lithium hydroxide and be selected from terephthalic acid or C
2～C
12At least a diprotic acid in the binary acid, encloses container, at 100 ℃～170 ℃, 0.1MPa carried out saponification reaction under the～0.6MPa 0.5～5.0 hour, the dehydration that heats up after the release adds surplus base oil circulation cooling, homogenizing, the degassing get final product, wherein the mol ratio of monoprotic acid and diprotic acid is 1: 0.1～0.8, and the add-on of calcium hydroxide is 5～50% of a monoprotic acid mole number, and the viscosifying agent consumption that acid-base reaction generates is 3～30% of a lubricating grease weight.
2. according to the described preparation method of claim 1, it is characterized in that, after the monoprotic acid dissolving, add calcium hydroxide earlier, reacted 5～20 minutes, add diprotic acid and lithium hydroxide again.
3. according to claim 1 or 2 described preparation methods, it is characterized in that saponification temperature is 110～160 ℃, pressure is 0.1～0.5MPa, and the reaction times is 0.6～3.0 hour.
4. according to claim 1 or 2 described preparation methods, it is characterized in that the mol ratio of monoprotic acid and diprotic acid is 1: 0.25～0.5.
5. according to claim 1 or 2 described preparation methods, it is characterized in that the add-on of calcium hydroxide is 5～30% of a monoprotic acid mole number.
6. according to claim 1 or 2 described preparation methods, it is characterized in that the amount of viscosifying agent is 5～25% of a lubricating grease weight.
7. according to claim 1 or 2 described preparation methods, it is characterized in that the consumption of water can be 3～5 times of alkali gross weight.
8. according to claim 1 or 2 described preparation methods, it is characterized in that base oil adds at twice, add 1/2～3/4 of gross weight in the reactant earlier, add the residue base oil after having reacted again to cool off.
9. according to claim 1 or 2 described preparation methods, it is characterized in that said monoprotic acid is 12-oxystearic acid or stearic acid, said diprotic acid is selected from terephthalic acid or C
4～C
12At least a acid in the binary acid.
10. according to claim 1 or 9 described preparation methods, it is characterized in that diprotic acid is selected from one of terephthalic acid, adipic acid, nonane diacid or sebacic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99107941A CN1087027C (en) | 1999-06-04 | 1999-06-04 | Process for preparing composite Li-Ca based grease |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99107941A CN1087027C (en) | 1999-06-04 | 1999-06-04 | Process for preparing composite Li-Ca based grease |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1276412A CN1276412A (en) | 2000-12-13 |
| CN1087027C true CN1087027C (en) | 2002-07-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99107941A Expired - Lifetime CN1087027C (en) | 1999-06-04 | 1999-06-04 | Process for preparing composite Li-Ca based grease |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008034959A1 (en) | 2008-07-25 | 2010-01-28 | Fuchs Petrolub Ag | Calcium / lithium complex fats and encapsulated constant velocity joint containing these and their application |
| CN104629882B (en) * | 2015-02-09 | 2018-05-01 | 新乡市恒星科技有限责任公司 | A kind of slowspeed machine bearing special grease and preparation method thereof |
| CN106497659A (en) * | 2016-10-05 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of turbine and worm lubricant composition and preparation method |
| CN108659922A (en) * | 2017-03-29 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of graphene lubricating grease and preparation method thereof |
| CN109054945A (en) * | 2018-07-23 | 2018-12-21 | 四川新驱科为科技有限公司 | A kind of high-fire resistance preparation of greases method |
| CN109251780A (en) * | 2018-10-11 | 2019-01-22 | 中国石油化工股份有限公司 | A kind of passenger car hub bearing lubricating grease composition and preparation method |
| CN115772435B (en) * | 2022-11-22 | 2024-02-27 | 中国石油化工股份有限公司 | Composite calcium type automobile hub bearing lubricating grease composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108442A (en) * | 1985-11-22 | 1987-06-03 | 中国石油化工总公司一坪化工厂 | Binary metallic based grease composition and preparation method thereof |
| US5350531A (en) * | 1992-07-30 | 1994-09-27 | Frey, The Wheelman, Inc. | Process for preparing a grease composition |
-
1999
- 1999-06-04 CN CN99107941A patent/CN1087027C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108442A (en) * | 1985-11-22 | 1987-06-03 | 中国石油化工总公司一坪化工厂 | Binary metallic based grease composition and preparation method thereof |
| US5350531A (en) * | 1992-07-30 | 1994-09-27 | Frey, The Wheelman, Inc. | Process for preparing a grease composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1276412A (en) | 2000-12-13 |
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Applicant after: China Petrochemical Group Corp. Applicant after: Sinopec Research Institute of Petroleum Processing Applicant before: China Petrochemical Group Corp. Applicant before: Chinese petrochemical industry Research Institute of Petro-Chemical Engineering of group company |
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Free format text: CORRECT: APPLICANT; FROM: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM + CHEMICAL CORPORATION, PETROLEUM CHEMICAL ENGINEERING INSTITUTE TO: CHINA PETROCHEMICAL CORPORATION; CHINA PETROCHEMICAL GROUP PETROCHEMICAL SINCE INSTITUTE |
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