CN102676276A - Process for preparing sulfurized calcium alkyl phenolate - Google Patents
Process for preparing sulfurized calcium alkyl phenolate Download PDFInfo
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- CN102676276A CN102676276A CN2012101664388A CN201210166438A CN102676276A CN 102676276 A CN102676276 A CN 102676276A CN 2012101664388 A CN2012101664388 A CN 2012101664388A CN 201210166438 A CN201210166438 A CN 201210166438A CN 102676276 A CN102676276 A CN 102676276A
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- sulfenyl phenolate
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Abstract
The invention discloses a process for preparing sulfurized calcium alkyl phenolate. The process includes the steps of Step 1, mixing alkylphenol with base oil by the mass ratio of (1:0.5)-(1:1.3) under the protection of nitrogen, adding sulphur, calcium oxide, calcium hydroxide, long-chain alkyl benzene sulfonic acid, long-chain fatty acid, long-chain fatty alcohol and polyisobutene succinic anhydride after mixing, dropwise adding glycol on a micro-negative pressure condition, and heating up to 180 DEG C slowly; Step 2, cooling materials in Step 1 to 105+/-5 DEG C, adding paint naphtha with the boiling point higher than 150 DEG C, and feeding carbon dioxide gas or carbon dioxide liquid at a temperature of 100-150 DEG C for 150-300 minutes; Step 3, subjecting reacted materials in Step 2 to vacuum distillation at 180-220 DEG C, and steaming out unreacted materials; and Step 4, cooling reacted materials in Step 3 to 100-120 DEG C, subjecting to centrifugation, adding 3%-8% of diatomite to centrifuged fluid for filtering, and obtaining red brown viscous materials which are the sulfurized calcium alkyl phenolate through filtering and refining.
Description
Technical field
The invention belongs to the metal detergent technical field, be specifically related to a kind of making method of calcium sulfenyl phenolate.
Background technology
Calcium sulfenyl phenolate is a kind of important metal detergent in the oil dope.It has stronger high temperature detergency, acid neutralization capacity, suppresses that carbon deposit generates, and certain performance such as anti-oxidant wear-resistant anticorrosive.The primary fundamental property of metal detergent is a colloidal stability, and colloidal stability is the basis that guarantees other performances of metal detergent, and therefore, the colloidal stability of calcium sulfenyl phenolate is most important.
Calcium sulfenyl phenolate by contain 10%～30% colloid lime carbonate with contain 25～35% be wrapped in that stable load micelle that the tensio-active agent on the carbonate surface forms and 10%～20% free surfactant molecule and micella thereof constituted.The load micelle that the tensio-active agent that upward wrap up on colloid lime carbonate and surface thereof is formed occupies the ratio about 60% in product; The particle diameter of this load micelle can not pass through semi-permeable membranes, and calcium sulfenyl phenolate role in lubricating oil is mainly provided by this micella.
In the allotment of multiple lubricating oil; Calcium sulfenyl phenolate is in harmonious proportion to base oil with other multiple additives; The consistency of itself and base oil and other additive is better; Yet thereby in lubricating oil, be widely used. in the storage process of lubricating oil, " falling calcium " phenomenon is ubiquitous phenomenon of lubricating oil industry and troubling insoluble problem.Research think the major cause of the generations phenomenon of " falling calcium " be since in the additive poor stability of colloid lime carbonate cause the stability of colloid lime carbonate and its colloidal particle diameter and to be adsorbed on the kind of the lip-deep tensio-active agent of lime carbonate in close relations in the additive.The particle diameter of colloid lime carbonate is adsorbed on the lip-deep tensio-active agent of colloid lime carbonate and comprises calcium sulfenyl phenolate, alkyl benzene calcium sulfonate, alkyl sodium salicylate, calcium naphthenate, allyl butyrate imide or the like between 0-100nm.Can produce deposition when having bibliographical information alkyl sodium salicylate and alkyl benzene calcium sulfonate in oil product, to coexist.The research document of relevant calcium sulfenyl phenolate colloidal stability is seldom seen.
Summary of the invention
The objective of the invention is to propose a kind of making method of calcium sulfenyl phenolate, its stability is high, and result of use is good.
In order to reach above-mentioned purpose of design, the technical scheme that the present invention adopts is following:
A kind of making method of calcium sulfenyl phenolate; In the mixture of alkylphenol and base oil, add tensio-active agent in proportion; Like alkyl benzene calcium sulfonate, alkyl sodium salicylate, calcium naphthenate, polyisobutylene succinic anhydride, can improve calcium sulfenyl phenolate micellar stability in the lubricating oil compound process like this;
Add long chain organic acid, long chain aliphatic alcohol or long chain organic acid salt, effectively synthesizing in proportion with colloid lime carbonate in the raising building-up process;
The content (2-5%) of moisture in the mixture in the strict control carbonation is with the resultant velocity of control colloid lime carbonate;
The feeding mode of carbonic acid gas and aeration time are with the particle size range of the colloid lime carbonate of control generation in the control building-up process; Make the colloid lime carbonate particle diameter of generation even, prevent to generate oarse-grained spherical calcium carbonate, reduce the generation of the colloid lime carbonate of 80-100nm particle size range; Provide convenience for purification step and (to adopt constant speed multiple spot venting method; Improve the dispersity of quicklime/calcium hydroxide and carbonic acid gas, make the colloid lime carbonate grain diameter of generation even) mostly at 20-60nm;
Reaction product cooling, centrifugal makes calcium sulfenyl phenolate; Through centrifugal mechanical impurity in the building-up process is removed, diatomite filtration is removed the colloid lime carbonate of particle diameter more than 80nm together, and the product turbidity is reached below the 10JTU.
Its making step is:
Step 1: under nitrogen protection; Alkylphenol and base oil mixed by the mass ratio of 1:0.5-1:1.3 (alkyl in the alkylphenol is most of to be replaced for single; Substituting group contains 9-24 carbon atom, is side chain and straight chain saturation alkane, and side chain accounts for 80-65%; Straight chain 20-35%, base oil are MO 100SN, 150SN or hydrocarbon synthesis oil or the synthetic ester lubricant suitable with it); Mix the back and add sulphur, quicklime, calcium hydroxide, chain alkyl Phenylsulfonic acid (carbochain contains 20-26 carbon atom), longer chain fatty acid, long chain aliphatic alcohol, polyisobutylene succinic anhydride; Under little condition of negative pressure, drip terepthaloyl moietie; Slowly be warming up to 180 ℃; Have hydrogen sulfide and emit, this reaction process is neutralization, vulcanization reaction;
Various compositions can add simultaneously also and can add at interval in the said step 1, and the ratio of concrete add-on is:
The mass ratio of alkylphenol and base oil is 1:0.5-1:1.3
The mass ratio of quicklime and calcium hydroxide is 1:0.1-1:0.5
The mol ratio of quicklime and alkylphenol is 1.3:1-3.8:1
The mol ratio of sulphur and alkylphenol is 1.5:1-3.0:1
The mol ratio of terepthaloyl moietie and alkylphenol is 1.5:1-4:1
The mol ratio of longer chain fatty acid and alkylphenol is 1:6-1:11
The mol ratio of long chain aliphatic alcohol and alkylphenol is 1:10-1:20
The mass ratio of long chain aliphatic alcohol, chain alkyl Phenylsulfonic acid, polyisobutylene succinic anhydride is 2:1:1-5:1:1
Step 2, the step 1 material is cooled to 105 ± 5 ℃; Add boiling point and be higher than 150 ℃ varnish makers' and painters' naphtha; The add-on of varnish makers' and painters' naphtha be the alkylphenol quality 1/2nd to sixth; Under 100-150 ℃ of condition, feed dioxide gas or liquid, the add-on of carbonic acid gas is quicklime and calcium hydroxide mole total amount 0.8 ~ 1.3 times, and aeration time is 150-300 minute;
Step 3, the step 2 reaction mass is carried out vacuum distilling, the distillation vacuum is lower than-0.094Mpa, temperature 180-220 ℃, steams the unreacted material;
Step 4, remaining material after the vacuum distilling is cooled to 100-120 ℃, through centrifugal, the liquid after centrifugal adds the 3%-8% diatomite filtration again, and is refining that the red-brown sticky material is a calcium sulfenyl phenolate through filtering.
Said longer chain fatty acid is the mixture of palmitic acid and/or stearic acid and/or 20 acid and/or behenic acid etc. or several kinds of acid.
Said long chain aliphatic alcohol is the mixture of hexadecanol and/or stearyl alcohol and/or eicosanol and/or behenyl alcohol etc. or several kinds of alcohol.
The beneficial effect of the making method of calcium sulfenyl phenolate of the present invention is: stability is high, and result of use is good.
Embodiment
Do further detailed description in the face of optimum implementation of the present invention down.
Embodiment 1:
In having four hole flasks of stirring, feed nitrogen protection, add 100 parts of alkylphenols successively, 50 parts of base oils, 30 parts of quicklime, 4 parts of calcium hydroxides, 20 parts of sulphur, 0.5 part of chain alkyl Phenylsulfonic acid, 10 parts of longer chain fatty acids, 8 parts of long chain aliphatic alcohols, 0.5 part of polyisobutylene succinic anhydride, 36 parts of terepthaloyl moietie; The open vacuum pump makes system keep little negative pressure, slowly is warming up to 180 ℃; Have hydrogen sulfide and emit, this gas is imported alkali lye absorb, after gas is emitted and finished; Be cooled to 100 ℃; Add 50 parts of solvent oils, feed atmospheric carbon dioxide, aeration time 150 minutes with 0.3 liter/minute flow velocity; Synthetic good material is carried out vacuum distilling, and the distillation vacuum is lower than-0.094Mpa, and 180 ℃ of temperature steam the unreacted material;
Remaining material after the vacuum distilling is cooled to 100 ℃,, adds 3% diatomite filtration again, promptly get the red-brown dope, i.e. calcium sulfenyl phenolate through sieve whizzer that crouches.
Embodiment 2
In having four hole flasks of stirring, feed nitrogen protection, add 100 parts of alkylphenols successively, 130 parts of base oils, 42 parts of quicklime, 5 parts of calcium hydroxides, 30 parts of sulphur, 2 parts of chain alkyl Phenylsulfonic acids, 12 parts of longer chain fatty acids, 8 parts of long chain aliphatic alcohols, 2 parts of succinyl oxides, 47 parts of terepthaloyl moietie; The open vacuum pump makes system keep little negative pressure, slowly is warming up to 180 ℃; Have hydrogen sulfide and emit, this gas is imported alkali lye absorb, after gas is emitted and finished; Be cooled to 105 ℃; Add 17 parts of solvent oils, feed atmospheric carbon dioxide, aeration time 300 minutes with 0.15 liter/minute flow velocity; Synthetic good material is carried out vacuum distilling, and the distillation vacuum is lower than-0.094Mpa, and 220 ℃ of temperature steam the unreacted material;
Remaining material after the vacuum distilling is cooled to 108 ℃,, adds 5% diatomite filtration again, promptly get the red-brown dope, i.e. calcium sulfenyl phenolate through sieve whizzer that crouches.
Embodiment 3
In having four hole flasks of stirring, feed nitrogen protection, add 100 parts of alkylphenols successively, 80 parts of base oils, 36 parts of quicklime, 5 parts of calcium hydroxides, 28 parts of sulphur, 3 parts of chain alkyl Phenylsulfonic acids, 12 parts of longer chain fatty acids, 9 parts of long chain aliphatic alcohols, 3 parts of succinyl oxides, 38 parts of terepthaloyl moietie; The open vacuum pump makes system keep little negative pressure, slowly is warming up to 180 ℃; Have hydrogen sulfide and emit, this gas is imported alkali lye absorb, after gas is emitted and finished; Be cooled to 110 ℃; Add 30 parts of solvent oils, feed atmospheric carbon dioxide, aeration time 240 minutes with 0.3 liter/minute flow velocity; Synthetic good material is carried out vacuum distilling, and the distillation vacuum is lower than-0.094Mpa, and 200 ℃ of temperature steam the unreacted material; Remaining material after the vacuum distilling is cooled to 110 ℃,, adds 8% diatomite filtration again, promptly get the red-brown dope, i.e. calcium sulfenyl phenolate through sieve whizzer that crouches.
The thermostability evaluation: product dissolves in the oil product with 10% ratio, in 105 ℃ of baking ovens, stored 7 days, and the record precipitation capacity, precipitation capacity is more little good more.
Home products stores 7 days mostly not to be had deposition or a spot of deposition is arranged, and it is obvious to store 30 days precipitation capacities, and external product stock does not have deposition after 7 days, and storing 14 days has the small amount of precipitate amount.The high stability calcium sulfenyl phenolate of the method development that provides through this patent stores 30 days is not had deposition.
The turbidity evaluation of product: according to detergent for lubricating oil tuurbidimetry SH/T 0028; Product dissolves in the base oil with 20% ratio; Turbidimeter detects, and the home products turbidity is many between 20-200JTU, and the external product turbidity is many between 20-80JTU; The high stability calcium sulfenyl phenolate turbidity of the method development that provides through this patent reaches below the 10JTU, and has stability to hydrolysis preferably.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and is convenient to these those skilled in the art and can understands and use the present invention, can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, and needn't pass through performing creative labour.Therefore, those skilled in the art should be within protection scope of the present invention to the simple modifications that the present invention makes according to announcement of the present invention.
Claims (7)
1. the making method of a calcium sulfenyl phenolate, it is characterized in that: its making step is:
Step 1: under nitrogen protection, alkylphenol is mixed with the mass ratio of base oil by 1:0.5-1:1.3; Mix the back and add sulphur, quicklime, calcium hydroxide, chain alkyl Phenylsulfonic acid, longer chain fatty acid, long chain aliphatic alcohol, polyisobutylene succinic anhydride drips terepthaloyl moietie under little condition of negative pressure, slowly be warming up to 180 ℃, has hydrogen sulfide to emit;
Various compositions can add simultaneously also and can add at interval in the said step 1, and the ratio of concrete add-on is:
The mass ratio of alkylphenol and base oil is 1:0.5-1:1.3;
The mass ratio of quicklime and calcium hydroxide is 1:0.1-1:0.5;
The mol ratio of quicklime and alkylphenol is 1.3:1-3.8:1;
The mol ratio of sulphur and alkylphenol is 1.5:1-3.0:1;
The mol ratio of terepthaloyl moietie and alkylphenol is 1.5:1-4:1;
The mol ratio of longer chain fatty acid and alkylphenol is 1:6-1:11;
The mol ratio of long chain aliphatic alcohol and alkylphenol is 1:10-1:20;
The mass ratio of long chain aliphatic alcohol, chain alkyl Phenylsulfonic acid, polyisobutylene succinic anhydride is 2:1:1-5:1:1;
Step 2, the step 1 material is cooled to 105 ± 5 ℃; Add boiling point and be higher than 150 ℃ varnish makers' and painters' naphtha; The add-on of varnish makers' and painters' naphtha be the alkylphenol quality 1/2nd to sixth; Under 100-150 ℃ of condition, feed dioxide gas or liquid, the add-on of carbonic acid gas is quicklime and calcium hydroxide mole total amount 0.8 ~ 1.3 times, and aeration time is 150-300 minute;
Step 3, the step 2 reaction mass is carried out vacuum distilling, the distillation vacuum is lower than-0.094Mpa, temperature 180-220 ℃, steams the unreacted material;
Step 4, remaining material after the vacuum distilling is cooled to 100-120 ℃, through centrifugal, the liquid after centrifugal adds the 3%-8% diatomite filtration again, and is refining that the red-brown sticky material is a calcium sulfenyl phenolate through filtering.
2. the making method of calcium sulfenyl phenolate according to claim 1, it is characterized in that: said longer chain fatty acid is palmitic acid and/or stearic acid and/or 20 acid and/or behenic acid.
3. the making method of calcium sulfenyl phenolate according to claim 1, it is characterized in that: said long chain aliphatic alcohol is hexadecanol and/or stearyl alcohol and/or eicosanol and/or behenyl alcohol.
4. the making method of calcium sulfenyl phenolate according to claim 1 is characterized in that: the alkyl in the said alkylphenol replaces for single, and substituting group contains 9-24 carbon atom, is side chain and straight chain saturation alkane, and side chain accounts for 80-65%, straight chain 20-35%.
5. the making method of calcium sulfenyl phenolate according to claim 1 is characterized in that: said base oil is MO 100SN, 150SN or hydrocarbon synthesis oil or the synthetic ester lubricant suitable with it.
6. the making method of calcium sulfenyl phenolate according to claim 1; It is characterized in that: in the step 4, the mechanical impurity in the building-up process is removed diatomite filtration through centrifugal; The colloid lime carbonate of particle diameter more than 80nm is removed together, the product turbidity is reached below the 10JTU.
7. the making method of calcium sulfenyl phenolate according to claim 1 is characterized in that: in the step 2, the mode that feeds carbonic acid gas is: constant speed multiple spot venting method.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101664388A CN102676276A (en) | 2012-05-25 | 2012-05-25 | Process for preparing sulfurized calcium alkyl phenolate |
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| CN2012101664388A CN102676276A (en) | 2012-05-25 | 2012-05-25 | Process for preparing sulfurized calcium alkyl phenolate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725358A (en) * | 2012-10-15 | 2014-04-16 | 中国石油化工股份有限公司 | Preparation method for vulcanized alkylphenol |
| CN105462652A (en) * | 2015-02-13 | 2016-04-06 | 新乡市瑞丰新材料股份有限公司 | Metal detergent, preparation method thereof, and lubricating oil containing metal detergent |
| WO2016127388A1 (en) * | 2015-02-13 | 2016-08-18 | 新乡市瑞丰新材料股份有限公司 | Calcium alkyl phenate sulfide and preparation method thereof, and lubricating oil comprising same |
| CN110257136A (en) * | 2019-05-09 | 2019-09-20 | 泉州市欧美润滑油制品有限公司 | General purpose type energy-saving environmental protection heavy load lubricating oil and preparation method thereof |
-
2012
- 2012-05-25 CN CN2012101664388A patent/CN102676276A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725358A (en) * | 2012-10-15 | 2014-04-16 | 中国石油化工股份有限公司 | Preparation method for vulcanized alkylphenol |
| CN103725358B (en) * | 2012-10-15 | 2015-07-01 | 中国石油化工股份有限公司 | Preparation method for vulcanized alkylphenol |
| CN105462652A (en) * | 2015-02-13 | 2016-04-06 | 新乡市瑞丰新材料股份有限公司 | Metal detergent, preparation method thereof, and lubricating oil containing metal detergent |
| WO2016127388A1 (en) * | 2015-02-13 | 2016-08-18 | 新乡市瑞丰新材料股份有限公司 | Calcium alkyl phenate sulfide and preparation method thereof, and lubricating oil comprising same |
| US20170051227A1 (en) * | 2015-02-13 | 2017-02-23 | Xinxiang City Ruifeng Chemical Co., Ltd | Metal detergent and preparation method thereof and lubricant oil containing metal detergent |
| EP3162877A4 (en) * | 2015-02-13 | 2018-01-10 | Xinxiang Richful Lube Additive Co., Ltd. | Calcium alkyl phenate sulfide and preparation method thereof, and lubricating oil comprising same |
| CN105462652B (en) * | 2015-02-13 | 2018-05-11 | 新乡市瑞丰新材料股份有限公司 | A kind of metal detergent and preparation method thereof and the lubricating oil containing the metal detergent |
| US9982212B2 (en) * | 2015-02-13 | 2018-05-29 | Xinxiang Richful Lube Additive Co., Ltd. | Metal detergent and preparation method thereof and lubricant oil containing metal detergent |
| CN110257136A (en) * | 2019-05-09 | 2019-09-20 | 泉州市欧美润滑油制品有限公司 | General purpose type energy-saving environmental protection heavy load lubricating oil and preparation method thereof |
| CN110257136B (en) * | 2019-05-09 | 2022-02-11 | 泉州市欧美润滑油制品有限公司 | Universal energy-saving environment-friendly heavy-load lubricating oil and preparation method thereof |
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Application publication date: 20120919 |