阅读说明：本技术 二聚酸抗磨剂组合物及其制备方法和应用 (Dimer acid antiwear agent composition and preparation method and application thereof ) 是由 陶志平 赵杰 伏朝林 于 2019-09-23 设计创作，主要内容包括：本发明提供一种二聚酸抗磨剂组合物及其制备方法和应用,抗磨剂组合物包含主剂和复配剂,主剂为二聚酸,复配剂选自芳烃溶剂或烯烃溶剂中的一种或多种；其中,二聚酸包含无环二聚酸、单环二聚酸和双环二聚酸中的一种或多种,单环二聚酸占二聚酸含量的60wt％以上。该二聚酸抗磨剂组合物中,二聚酸的单环占比高,有效提高了抗磨性能,相比于传统抗磨剂具有较大优势,可用作燃料的抗磨剂,尤其是用于航空燃料领域。此外,在达到相同抗磨效果的情况下,更节约抗磨剂的使用量,大大节约了生产成本,具有良好的工业应用前景。(The invention provides a dimer acid antiwear agent composition and a preparation method and application thereof, wherein the antiwear agent composition comprises a main agent and a compound agent, the main agent is dimer acid, and the compound agent is selected from one or more of aromatic hydrocarbon solvent or olefin solvent; wherein the dimer acid comprises one or more of acyclic dimer acid, monocyclic dimer acid and bicyclic dimer acid, and the content of the monocyclic dimer acid is more than 60 wt% of the content of the dimer acid. In the dimer acid antiwear agent composition, the single-ring occupancy ratio of dimer acid is high, the antiwear performance is effectively improved, and compared with the traditional antiwear agent, the dimer acid antiwear agent composition has great advantages, can be used as an antiwear agent of fuel, and is particularly used in the field of aviation fuel. In addition, under the condition of achieving the same anti-wear effect, the consumption of the anti-wear agent is saved, the production cost is greatly saved, and the method has a good industrial application prospect.)

1. The dimer acid antiwear agent composition is characterized by comprising a main agent and a compound agent, wherein the main agent is dimer acid, and the compound agent is selected from one or more of aromatic hydrocarbon solvent or olefin solvent; the dimer acid comprises one or more of acyclic dimer acid, monocyclic dimer acid and bicyclic dimer acid, and the content of the monocyclic dimer acid is more than 60 wt% of the content of the dimer acid.

2. The dimer acid antiwear agent composition of claim 1 wherein the dimer acid has an olefin content of no greater than 50%.

3. The dimer acid antiwear agent composition according to claim 1, wherein the main agent is present in an amount of 40 wt% to 80 wt%, and the combination agent is present in an amount of 20 wt% to 60 wt%.

4. The dimer acid antiwear agent composition according to claim 1, wherein the dimer acid comprises 5 to 40 wt% of the dimer acid content, and the dimer acid comprises 5 to 40 wt% of the dimer acid content.

5. The dimer acid antiwear agent composition of claim 1 wherein the antiwear agent composition further comprises an antioxidant.

6. The dimer acid antiwear agent composition of claim 5, wherein the antioxidant is 2.6-di-tert-butyl-p-methylphenol, and the antioxidant comprises 0.5 wt% to 2.0 wt% of the dimer acid content.

7. The dimer acid antiwear agent composition according to claim 1, wherein the aromatic hydrocarbon solvent is selected from one or more of xylene and tetralin, and the olefin solvent is selected from one or more of decene and undecene.

8. A method for preparing the dimer acid antiwear agent composition defined in any one of claims 1-7, comprising:

with C₁₈The fatty acid is used as a raw material, and the raw material is contacted with a catalyst and heated to react to generate the dimer acid;

uniformly mixing the dimer acid and the compound agent to obtain the dimer acid antiwear agent composition;

the catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component contains aluminum, the carrier is an MCM-41 molecular sieve or an MCM-48 molecular sieve, and the silica-alumina ratio of the catalyst is (5-80): 1 in terms of molar ratio.

9. The preparation method of claim 8, wherein the silicon-aluminum ratio of the catalyst is (20-40): 1.

10. The method of claim 8, wherein the active component further comprises M, wherein M is one or more selected from lithium, boron, calcium and phosphorus, and the active component M accounts for no more than 1.2 wt% of the catalyst.

11. The preparation method according to claim 10, wherein the active component M accounts for 0.6-0.9 wt% of the catalyst.

12. The method of claim 8, wherein the reaction is carried out under a carbon dioxide atmosphere.

13. The method according to claim 8, wherein C is₁₈The fatty acid is tall oil fatty acid, oleic acid or linoleic acid.

14. The method according to claim 8, wherein the catalyst is present in an amount of 5 to 20 wt% based on the content of the raw material.

15. The preparation method according to claim 8, wherein the reaction temperature is 200-270 ℃, the reaction pressure is 0.5-2 MPa, and the reaction time is 3-8 h.

16. The method of manufacturing according to claim 8, further comprising:

adding a solvent into the product obtained after the reaction to form crude dimer acid feed liquid;

carrying out catalyst removal treatment on the crude dimer acid feed liquid, and recycling a solid product obtained after treatment as the catalyst;

and carrying out molecular distillation treatment on the feed liquid subjected to catalyst removal treatment to obtain the dimer acid.

17. The method according to claim 16, wherein the molecular distillation treatment comprises a primary molecular distillation and a secondary molecular distillation performed in this order, wherein the primary molecular distillation has a distillation temperature of 100 ℃ to 180 ℃ and a pressure of 1Pa to 5 Pa; the distillation temperature of the secondary molecular distillation is 180-280 ℃, and the pressure is 1-5 Pa.

18. The method according to claim 8, further comprising hydrogenating the dimer acid before mixing the dimer acid with the compounded formulation.

19. The method of claim 18, wherein the hydrogenation reaction comprises: under the conditions that the reaction temperature is 120-160 ℃ and the hydrogen pressure is 0.5-3.0 MPa, the dimer acid and the hydrogenation catalyst are in contact reaction;

the hydrogenation catalyst is a Raney nickel catalyst or a supported transition metal catalyst, the supported transition metal catalyst comprises a carrier and an active component loaded on the carrier, the carrier is selected from active carbon or aluminum oxide, and the active component is selected from one or more of palladium, platinum, ruthenium, rhodium, iridium, nickel and copper.

20. Use of the dimer acid antiwear agent composition according to any one of claims 1 to 7 in the fuel field.

Technical Field

The invention relates to the technical field of antiwear agents, and particularly relates to a dimer acid antiwear agent composition and application thereof.

Background

Dimer acid, commonly referred to as dimer fatty acid, is a complex mixture of ingredients, so called because the major constituent contains two carboxylic acid groups. At present, dimer acid is widely applied to the fields of synthetic printed circuit board materials, ink manufacturing, rocket motor materials and the like. In addition, the dimer acid also has stronger polarity, is easy to adsorb on the surface of metal to form an oil film, and effectively reduces the friction and the abrasion of metal parts, so the dimer acid has excellent lubricity and abrasion resistance, can be used as an anti-wear agent of fuel, and is particularly used in the field of aviation fuel.

At present, jet fuel antiwear agents abroad are mainly dimer acid type, and naphthenic acid type antiwear agents are mainly used at home. The naphthenic acid is mainly derived from diesel oil and aviation kerosene, but the sources of the natural naphthenic acid are increasingly limited as refineries begin to adopt hydrogenation processes to refine the diesel oil and the aviation kerosene. Therefore, there is an increasing demand for dimer acid-based antiwear agents from an international standpoint as well as from a raw material source.

The main agent of the dimer acid antiwear agent is dimer acid, but the existing dimer acid synthesis method has the problems of difficult separation, difficult regeneration, high cost, low yield of the dimer acid and the like, so that the development of the dimer acid antiwear agent is limited. In addition, when dimer acid synthesized by the existing method is used as an antiwear agent, the antiwear effect is not ideal.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The main purpose of the present invention is to overcome at least one of the above drawbacks of the prior art, and to provide a dimer acid antiwear agent composition, and a preparation method and an application thereof, in which the dimer acid antiwear agent composition has a high monocyclic ratio of dimer acid, effectively improves the antiwear performance, has a great advantage compared to the conventional antiwear agents, and can be used as an antiwear agent for fuel, especially in the field of aviation fuel. In addition, under the condition of achieving the same anti-wear effect, the consumption of the anti-wear agent is saved, the production cost is greatly saved, and the method has a good industrial application prospect.

In order to realize the purpose of the invention, the following technical scheme is adopted:

the invention provides a dimer acid antiwear agent composition on one hand, which comprises a main agent and a compound agent, wherein the main agent is dimer acid, and the compound agent is selected from one or more of aromatic hydrocarbon solvent or olefin solvent; wherein the dimer acid comprises one or more of acyclic dimer acid, monocyclic dimer acid and bicyclic dimer acid, and the content of the monocyclic dimer acid is more than 60 wt% of the content of the dimer acid.

According to one embodiment of the present invention, the olefin content of the dimer acid is no greater than 50%.

According to one embodiment of the invention, the content of the main agent is 40 wt% to 80 wt%, and the content of the compound agent is 20 wt% to 60 wt%.

According to one embodiment of the present invention, the dimer acid contains 5 to 40 wt% of acyclic dimer acid and 5 to 40 wt% of bicyclic dimer acid.

According to one embodiment of the invention, the antiwear agent composition further comprises an antioxidant.

According to one embodiment of the invention, the antioxidant is 2.6-di-tert-butyl-p-methylphenol, and the antioxidant accounts for 0.5-2.0 wt% of the content of the dimer acid.

According to one embodiment of the present invention, the aromatic hydrocarbon solvent is selected from one or more of xylene and tetralin, and the olefin solvent is selected from one or more of decene and undecene.

In another aspect, the present invention provides a preparation method of the dimer acid antiwear agent composition, including:

with C₁₈The fatty acid is used as a raw material, and the raw material is contacted with a catalyst and heated to react to generate dimer acid; uniformly mixing dimer acid and a compound agent to obtain a dimer acid antiwear agent composition; wherein the catalyst comprises a carrier and is loaded on the carrierThe active component of the catalyst body comprises aluminum, and the carrier is an MCM-41 molecular sieve or an MCM-48 molecular sieve, wherein the silica-alumina ratio of the catalyst is (5-80): 1 in terms of molar ratio.

According to one embodiment of the invention, the silicon-aluminum ratio of the catalyst is (20-40): 1.

According to one embodiment of the invention, the active component further comprises M, wherein M is selected from one or more of lithium, boron, calcium and phosphorus, and the active component M accounts for not more than 1.2 wt% of the catalyst.

According to one embodiment of the invention, the active component M represents between 0.6% and 0.9% by weight of the catalyst content.

According to one embodiment of the invention, the reaction is carried out under an atmosphere of carbon dioxide.

According to one embodiment of the invention, C₁₈The fatty acid is tall oil fatty acid, oleic acid or linoleic acid.

According to one embodiment of the invention, the catalyst comprises 5 wt% to 20 wt% of the feed content.

According to one embodiment of the invention, the reaction temperature is 200-270 ℃, the reaction pressure is 0.5-2 MPa, and the reaction time is 3-8 h.

According to an embodiment of the present invention, the preparation method further comprises: adding a solvent into a product obtained after the reaction to form a crude dimer acid feed liquid; carrying out catalyst removal treatment on the crude dimer acid feed liquid, and recycling a solid product obtained after treatment as a catalyst; and (4) carrying out molecular distillation treatment on the feed liquid after catalyst removal treatment to obtain the dimer acid.

According to one embodiment of the invention, the molecular distillation treatment comprises a primary molecular distillation and a secondary molecular distillation which are sequentially carried out, wherein the distillation temperature of the primary molecular distillation is 100-180 ℃, and the pressure is 1-5 Pa; the distillation temperature of the secondary molecular distillation is 180-280 ℃, and the pressure is 1-5 Pa.

According to an embodiment of the present invention, the method further comprises hydrogenation of the dimer acid before mixing the dimer acid with the compound.

According to one embodiment of the invention, the hydrogenation reaction comprises: under the conditions that the reaction temperature is 120-160 ℃ and the hydrogen pressure is 0.5-3.0 MPa, the dimer acid and the hydrogenation catalyst are in contact reaction;

the hydrogenation catalyst is a Raney nickel catalyst or a supported transition metal catalyst, the supported transition metal catalyst comprises a carrier and an active component loaded on the carrier, the carrier is selected from active carbon or aluminum oxide, and the active component is selected from one or more of palladium, platinum, ruthenium, rhodium, iridium, nickel and copper.

In a further aspect the present invention provides the use of a dimer acid antiwear agent composition as described above in the fuel field.

According to the technical scheme, the dimer acid antiwear agent composition, the preparation method and the application thereof have the advantages and positive effects that:

the dimer acid antiwear agent composition provided by the invention contains a main agent dimer acid and a compound agent, wherein the monocyclic proportion of the main agent dimer acid is high, and the wear resistance of the dimer acid antiwear agent composition is improved. The adopted compound agent can form a synergistic effect, and the abrasion resistance is further integrally improved, so that the dimer acid antiwear agent composition has greater advantages compared with the traditional antiwear agent, can be used as an antiwear agent of fuel, and is particularly used in the field of aviation fuel. The dimer acid antiwear agent composition has a simple preparation method, particularly the main agent dimer acid is prepared by adopting a specific catalyst and a specific method, and the purity, the yield and the selectivity of the obtained dimer acid are high, so that when the dimer acid antiwear agent composition is added into fuel to improve the antiwear property, the consumption of an antiwear agent is saved under the condition of achieving the same antiwear effect, the production cost is greatly saved, and the dimer acid antiwear agent composition has a good industrial application prospect.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.

FIG. 1 is an IR spectrum of dimer acid of example 1 of this invention.

Detailed Description

The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.

The invention provides a dimer acid antiwear agent composition on one hand, which comprises a main agent and a compound agent, wherein the main agent is dimer acid, and the compound agent is selected from one or more of aromatic hydrocarbon solvent or olefin solvent; wherein the dimer acid comprises one or more of acyclic dimer acid (shown as formula I), monocyclic dimer acid (shown as formula II) and bicyclic dimer acid (shown as formula III), and the content of the monocyclic dimer acid is more than 60 wt% of the content of the dimer acid. In some embodiments, the dimer acid comprises 5 wt% to 40 wt% of acyclic dimer acid and 5 wt% to 40 wt% of dimer acid.

Compared with naphthenic acid type antiwear agents, dimer acid antiwear agents have excellent lubricity and abrasion resistance, and have better industrial application prospects in the future in consideration of the angle of connection with international jet fuel antiwear agents. The dimer acid antiwear agent is a dimer acid as a main agent, and a great deal of research has been carried out on the synthesis of the dimer acid, but clay is mostly used as a polymerization catalyst. The preparation process of the argil as the catalyst is mature, but the argil has the defects of adsorbing a certain amount of dimer acid products, being difficult to regenerate, large solid waste generation amount and the like. The dimer acid synthesized by adopting other catalysts has the problems of difficult separation, difficult regeneration, high cost, low yield of the dimer acid and the like, so that the development of the dimer acid antiwear agent is limited. In addition, when dimer acid synthesized by the existing method is used as an antiwear agent, the antiwear effect is not ideal.

Dimer acids typically comprise acyclic, monocyclic and bicyclic C in composition₃₆Unsaturated fatty acids. The inventor of the invention finds that the content of the single ring in the dimer acid is controlled to be more than 60 wt% of the content of the dimer acid, so that the flexibility of the dimer acid is improved, the friction coefficient of the dimer acid is reduced, the abrasion resistance of the dimer acid can be effectively improved, and the performance of the dimer acid antiwear agent is improved. In addition, dimer acid has a high viscosity, and when used as an antiwear agent, it is necessary to dilute it with a compounding agent to use it as an antiwear agent. The requirements of the compound agent require that the compound agent has better dissolving capacity, can be mutually dissolved with dimer acid, and can form a synergistic effect with the dimer acid, so that the integral abrasion resistance is improved, and no negative influence is brought to the oil material. Through a large number of experiments, the inventor surprisingly finds that the synergistic effect can be realized by adopting the aromatic hydrocarbon solvent or the olefin solvent as the compound agent, so that the anti-wear performance is further improved, and meanwhile, no negative influence is brought. Therefore, the antiwear agent composition with good abrasion resistance and high quality is obtained by combining the main agent and the compound agent, and has good industrial application prospect when being used as an antiwear agent.

In some embodiments, the olefin content of the foregoing dimer acid is no greater than 50%. Dimer acid contains a large amount of unsaturated fatty acids, and the higher the degree of unsaturation in the molecule, the larger the friction coefficient, thereby affecting the abrasion resistance. The proper hydrofining is carried out on the dimer acid, so that the olefin content is reduced, the saturation degree is increased, the adsorption energy is increased, and the anti-wear effect of the dimer acid can be effectively improved. In addition, the dimer acid after hydrorefining can improve the lubricity of the fuel, and is particularly suitable for the field of jet dyes.

In some embodiments, the dimer acid as the main agent is present in an amount of 40 wt% to 80 wt%, preferably 50 wt% to 70 wt%, and the combination agent is present in an amount of 20 wt% to 60 wt%. Too high or too low a dimer acid content will reduce the overall performance of the composition. The compound agent is selected from aromatic hydrocarbon solvent or olefin solvent, wherein the aromatic hydrocarbon solvent includes but is not limited to xylene, tetrahydronaphthalene and the like, and the olefin solvent includes but is not limited to decene, undecene and the like.

In some embodiments, the antiwear agent composition further comprises an antioxidant. Preferably, the antioxidant is 2.6-di-tert-butyl-p-methylphenol, and the antioxidant accounts for 0.5-2.0 wt% of the content of the dimer acid. Since dimer acid itself contains more unsaturated bonds, which as an acidic substance affects the stability of fuel, especially jet fuel, it is necessary to add a certain amount of antioxidant to improve the overall performance of the anti-wear agent.

In another aspect, the present invention provides a preparation method of the dimer acid antiwear agent composition, including:

with C₁₈The fatty acid is used as a raw material, and the raw material is contacted with a catalyst and heated to react to generate dimer acid; uniformly mixing dimer acid and a compound agent to obtain a dimer acid antiwear agent composition; the catalyst comprises a carrier and an active component loaded on the carrier, wherein the active component contains aluminum, the carrier is an MCM-41 molecular sieve or an MCM-48 molecular sieve, and the silica-alumina ratio of the catalyst is (5-80): 1, preferably (20-40): 1 in terms of molar ratio.

The inventor of the invention finds that the dimer acid can be effectively synthesized by adopting the molecular sieve catalyst loaded with specific components and active components with specific content, and the purity, yield and selectivity of the obtained dimer acid are obviously improved. Wherein, the aluminum can make the catalyst have certain acidity and catalyze the olefin to carry out polymerization reaction. The molecular sieve is an MCM-41 molecular sieve or an MCM-48 molecular sieve, and is preferably the MCM-41 molecular sieve. The molecular sieve has the aperture range of 4-8 nm, and has rich mesoporous structure and large specific surface area (800 m)²/g-1000m²The mesoporous material of/g) enables aluminum to have acidic active sites after being added, can better perform catalytic polymerization, and is particularly beneficial to enabling the monocyclic ratio of the synthesized dimer acid to be higher when the mesoporous material is used for synthesizing the dimer acid, thereby being beneficial to improving the abrasion resistance of the dimer acid. By adjustingThe silica to alumina ratio in the molecular sieve can affect the acid content of the catalyst, and further affect the catalytic activity of the catalyst. The inventor finds that the silicon-aluminum ratio of the catalyst of the invention is too large or too small, which affects the selectivity and yield of the dimer acid, and the silicon-aluminum ratio is preferably (5-80): 1, preferably (20-40): 1.

In some embodiments, the active component of the catalyst of the present invention further comprises M, wherein M is selected from one or more of lithium (Li), boron (B), calcium (Ca) and phosphorus (P), and the active component M accounts for not more than 1.2 wt% of the catalyst, preferably 0.6 wt% to 0.9 wt%. The introduction of the active component M can play a synergistic role with Al, and the acidity and the acid content of the catalyst can be changed by adjusting the content of the specific active component M, so that the catalyst is suitable for catalyzing the synthesis of dimer acid; in addition, the active component M also has a certain auxiliary agent effect and can induce or promote diene synthesis reaction, and further, the catalyst also has the advantages of easy recovery and recycling.

Another aspect of the present invention provides a method for preparing the above catalyst, comprising: adding a template agent and a silicon source into water, and uniformly stirring to obtain an initial gel mixture; adding an aluminum source, namely an aqueous solution containing an active component aluminum, such as aluminum sulfate, into the initial gel mixture, stirring and adjusting the pH value of the solution to 10-11 to obtain a gel precursor; heating the gel precursor for crystallization; after crystallization treatment, separating a crystallized solid product from a mother solution; and washing, drying and calcining the crystallized solid product to obtain the catalyst.

The invention also comprises adding a compound of active ingredient M to the initial gel mixture, wherein the compound of active ingredient M is selected from one or more of the chloride, hydroxide and carbonate compounds of M, M is selected from one or more of lithium, boron, calcium and phosphorus.

The hydrothermal synthesis method is adopted to dope M into the catalyst, so that the loading effect of the active component M is more stable, the dispersion is better, and compared with an impregnation method or an ion exchange method, the catalyst prepared by the method is more suitable for repeated cyclic utilization.

The aforementioned templating agents include, but are not limited to, one or more of cetyltrimethylammonium bromide (CTAB), tetrapropylammonium bromide, and tetraethylammonium bromide, and the silicon source includes, but is not limited to, one or more of Tetraethylorthosilicate (TEOS), solid amorphous silica, and sodium silicate. Preferably, the templating agent is cetyltrimethylammonium bromide and the silicon source is Tetraethylorthosilicate (TEOS).

In some embodiments, the active ingredient M is lithium and the compound containing the active ingredient M is selected from the group consisting of lithium chloride (LiCl), lithium carbonate (Li)₂CO₃) And lithium hydroxide (LiOH). Preferably, lithium chloride (LiCl).

According to the invention, the crystallization temperature and crystallization time have a certain influence on the catalyst synthesized. The crystallization temperature should not be too high or too low, and the time should not be too short or too long, which would result in a certain degree of catalyst performance degradation. In some embodiments, the temperature of the crystallization treatment is 120 ℃ to 160 ℃, preferably 130 ℃ to 150 ℃, and the time of the crystallization treatment is 18h to 30h, preferably 20h to 24 h.

In some embodiments, the aforementioned calcining comprises: calcining at 450-650 ℃ for 8-14 h at the heating rate of 2-5 ℃/min. Preferably, the heating rate is 3 ℃/min to 4 ℃/min, the calcining temperature is 500 ℃ to 600 ℃, and the calcining time is 10h to 12 h.

In the catalytic reaction for the preparation of dimer acid according to the present invention, the aforementioned C₁₈The fatty acid may be tall oil fatty acid, oleic acid or linoleic acid, preferably tall oil fatty acid. The oleic acid or linoleic acid can be derived from the transformation of vegetable oil and fat, including soybean oil, corn oil, sunflower seed oil, peanut oil, cottonseed oil, rapeseed oil, sesame oil, palm oil, coconut oil, castor oil and the like, and can also be synthetic oleic acid or linoleic acid, which is not limited in the invention.

In some embodiments, when vegetable oil acid is used as the raw material, ethanol, water, and sodium hydroxide (NaOH) are added to perform saponification in a hydrolysis reactor at a temperature of 70 ℃. In some embodiments, the mass ratio of the vegetable oil acid, the ethanol, the water and the sodium hydroxide is (1-2): 0.5-1): 0.05-0.5. After completion of the saponification reaction, phosphoric acid is subsequently addedAcidifying until pH is 2-3, extracting with petroleum ether of the same volume, collecting the upper layer to obtain oil phase of mixture of petroleum ether and mixed fatty acid, washing the oil phase with water, drying with anhydrous magnesium sulfate, distilling under reduced pressure to remove petroleum ether, and vacuum drying to obtain C₁₈Mixing the fatty acids.

According to the present invention, the concentration of the catalyst in the reaction system is different, and the yield of dimer acid is affected to a certain extent. When the catalyst content is too low, the fatty acid conversion rate is lowered, resulting in a decrease in yield. The increase of the catalyst content will affect the selectivity of dimer acid and increase the cost. In some embodiments, the catalyst of the present invention comprises from 5 wt% to 20 wt%, preferably from 10 wt% to 15 wt% of the feed content.

In some embodiments, the catalytic reaction temperature is 200 ℃ to 270 ℃, preferably 240 ℃ to 250 ℃. The yield and selectivity of dimer acid can be influenced by over-high catalytic reaction temperature, and the yield can be influenced by reducing the conversion rate of fatty acid to a certain extent by over-low temperature.

In some embodiments, the catalytic reaction time is 3 to 8 hours, preferably 6 to 8 hours. Too long or too short a catalytic reaction time will affect the yield and selectivity of dimer acid.

In some embodiments, the catalytic reaction is preferably carried out under an atmosphere of carbon dioxide. The side reaction of decarboxylation is easy to occur in the polymerization process of the dimer acid, which causes the problems of the yield reduction and the increase of the by-products of the dimer acid. By adopting the reaction atmosphere of carbon dioxide, the decarboxylation side reaction can be effectively inhibited, so that the yield of dimer acid is improved, and the generation of byproducts is reduced.

In some embodiments, the reaction pressure is from 0.5MPa to 2MPa, preferably from 0.8MPa to 1.2MPa, more preferably 1 MPa. The yield and selectivity of dimer acid are affected to different degrees by too high or too low a reaction pressure.

In some embodiments, the aforementioned preparation method further comprises a catalyst removal and purification process, in particular: adding solvents such as petroleum ether and the like into the product obtained after the reaction to form crude dimer acid feed liquid; carrying out catalyst removal treatment on the crude dimer acid feed liquid, and recycling a solid product obtained after treatment as a catalyst; and (3) carrying out molecular distillation treatment on the feed liquid subjected to catalyst removal treatment to obtain the dimer acid.

In some embodiments, the foregoing de-catalysis treatment may be by centrifugation. For example, an equal volume of petroleum ether is added to the reaction product to form a dimer acid feed, which is then centrifuged to remove the catalyst. And further washing with deionized water of 70-80 deg.c in twice the volume of the dimer acid liquid, and separating to obtain catalyst eliminated dimer acid liquid for reuse. In some embodiments, the recovered catalyst can be ultrasonically washed by isopropanol or ethanol at 50 ℃ for about 1h, and then dried at 100 ℃ for 10h to obtain the recyclable catalyst.

The dimer acid feed liquid after the catalyst removal can be further dried over anhydrous magnesium sulfate overnight, the anhydrous magnesium sulfate is filtered, then the dimer acid feed liquid is subjected to reduced pressure distillation to remove petroleum ether, and the obtained product can be further subjected to molecular distillation treatment to obtain the high-purity dimer acid.

In some embodiments, the molecular distillation process comprises a primary molecular distillation and a secondary molecular distillation performed sequentially, wherein the primary molecular distillation has a distillation temperature of 100 ℃ to 180 ℃, preferably 130 ℃ to 160 ℃, and a pressure of 1Pa to 5Pa, preferably 3Pa to 4 Pa; the unreacted monoacid in the product can be separated by primary molecular distillation; and performing secondary molecular distillation on the product after the primary molecular distillation treatment, wherein the distillation temperature of the secondary molecular distillation is 180-280 ℃, preferably 200-250 ℃, and the pressure is 1-5 Pa, preferably 2-3 Pa. Secondary molecular distillation is used to separate unreacted monomer acid and excess reacted polyacid in the product.

In some embodiments, the present invention further comprises, before mixing the dimer acid with the compound, optionally hydrogenating the dimer acid by contacting the dimer acid with a hydrogenation catalyst to increase the saturation degree of the dimer acid, increase the adsorption energy of the dimer acid, and increase the anti-wear performance of the dimer acid.

The hydrofining reaction can be carried out in a high-pressure reaction kettle withWith mechanical stirring, the reaction temperature is 120-160 ℃, preferably 130-150 ℃; h₂The pressure is 0.5MPa to 3.0MPa, preferably 1.0MPa to 2.0 MPa. The hydrogenation catalyst is Raney nickel catalyst or supported transition metal catalyst, the supported transition metal catalyst comprises a carrier and an active component loaded on the carrier, and the carrier is selected from active carbon or aluminum oxide (Al)₂O₃) The active component is selected from one or more of palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), iridium (Ir), nickel (Ni) and copper (Cu). It should be noted that the present invention is not limited to the above-mentioned hydrogenation conditions, and all hydrogenation methods capable of achieving a desired olefin content of the dimer acid are within the scope of the present invention.

The method is adopted to prepare the dimer acid, so that the purity of the dimer acid product can reach more than 95 percent, and in addition, the yield can also reach higher while the selectivity of the product is ensured. The dimer acid antiwear agent prepared by the dimer acid has good antiwear performance, and the compounding agent can realize the effect of synergistically increasing the antiwear performance.

The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, all reagents used in the invention are analytically pure.

Preparation example 1

This preparation example 1 is intended to illustrate the preparation of the catalyst of the present invention

(1) Dissolving 10g of cetyltrimethylammonium bromide (CTAB) template agent in 50mL of deionized water, and fully stirring for 10min at 50 ℃ until the solution becomes a transparent gel solid state;

(2) then, 44mL of tetraethyl orthosilicate (TEOS) was added thereto and mixed, and stirred at normal temperature for 30min to obtain an initial gel mixture;

(3) according to the requirement of Si/Al-40, Al with the concentration of 0.243mol/L is added₂(SO₄)₃10mL of aqueous solution; then according to the requirement of Li doping amount of 0.9 wt%, adding 15mL of 1.0mol/L LiCl solution as a lithium source, and stirring for about 30min to obtain a white colloidal solution;

(4) adjusting pH to 10-11 with strong ammonia water, and stirring for 60 min;

(5) transferring the mixture into a stainless steel reactor with a polytetrafluoroethylene lining, sealing, and crystallizing for 24 hours in an oven at the crystallization temperature of 140 ℃;

(6) after crystallization is finished, filtering and separating the crystallized solid product from mother liquor, and repeatedly washing the crystallized solid product to be neutral by using deionized water;

(7) drying at 80 deg.C for 12h to obtain dried solid product;

(8) and finally, calcining the mixture in a muffle furnace at 550 ℃ for 10 hours at the heating rate of 2 ℃/min to obtain the Li-Al-MCM-41 molecular sieve.

Example 1

This example 1 is intended to illustrate the preparation of a dimer acid antiwear agent composition of the present invention using the catalyst of preparation example 1.

(1) Preparation of dimer acid

Weighing 100g of tall oil fatty acid as a raw material, adding the raw material into a 300mL high-pressure reaction kettle, adding 15 wt% of the catalyst of the preparation example 1 based on the reaction raw material, and introducing CO into the reaction kettle₂Air in the gas replacement kettle is replaced for three times, and then CO is introduced₂And (3) heating the gas to 1MPa, then heating to the reaction temperature of 240 ℃, and reacting for 6 hours to obtain the crude dimer acid. Adding petroleum ether with the same volume into the reaction product to form dimer acid feed liquid, and then centrifugally separating the dimer acid feed liquid to remove the catalyst; washing with deionized water of 80 ℃ which is twice as much as the volume of the dimer acid feed liquid, separating the lower layer of deionized water to obtain the dimer acid feed liquid, drying over night with anhydrous magnesium sulfate, filtering out the anhydrous magnesium sulfate, and distilling the dimer acid feed liquid under reduced pressure to remove petroleum ether to obtain the dimer acid. The dimer acid is subjected to two-stage molecular distillation to obtain high-purity dimer acid, the first-stage operation temperature is 150 ℃, the operation pressure is 4Pa, and the high-purity dimer acid is used for separating unreacted monomer acid; the second-stage operation temperature is 240 ℃, the operation pressure is 2Pa, the second-stage operation temperature is used for separating the dimer acid, the yield of the dimer acid reaches 77.4 percent and the purity of the dimer acid product reaches over 95 percent through liquid chromatography analysis after two-stage molecular distillation.

The structure distribution of the dimer acid obtained was measured and the infrared results are shown in FIG. 1. Wherein the proportion of the monocyclic dimer acid is 70%, the proportion of the bicyclic dimer acid is 15%, and the proportion of the acyclic dimer acid is 15%.

(2) Preparation of dimer acid antiwear agent composition

Compounding the dimer acid and the tetrahydronaphthalene in the step (1), wherein the mass percent of the dimer acid is 60 wt%, adding 1.0 wt% of 2.6-di-tert-butyl-p-methylphenol, and uniformly mixing to obtain the dimer acid antiwear agent composition.

Examples 2 to 3

A dimer acid antiwear agent composition was prepared according to the method of example 1, except that the raw materials added in step (1) were changed separately, and the specific results are tabulated below in Table 1:

TABLE 1

Therefore, the yield and the structural distribution of the dimer acid can be influenced by adopting different raw materials for preparing the dimer acid, and in view of the combination, the tall oil fatty acid is preferably adopted as the raw material.

Examples 4 to 7

A dimer acid antiwear agent composition was prepared according to the method of example 1, except that the silica to alumina ratio of the catalyst used in step (1) was varied, as specified in Table 2 below:

TABLE 2

As can be seen from Table 2 above, the difference in Si/Al ratio has an effect on the structural distribution of the dimer acid product. Preferably, when the Si/Al ratio is (20-40): 1, the selectivity, yield and monocyclic ratio of the dimer acid are relatively high.

Comparative examples 1 to 2

Dimer acid was prepared according to the procedure of example 1, except that clay (enokay technologies, ltd), ZSM-5(Si/Al ═ 40, nankai catalyst factory) were used instead of the catalyst of the present invention, respectively, to prepare dimer acid, the results of which are shown in the following table 3:

TABLE 3

From the above table 3, it can be seen that the catalyst of the present invention has a higher yield than other existing catalysts, and the dimer acid monocyclic ratio is up to 70 wt%, which is beneficial to improving the flexibility of dimer acid and reducing the friction coefficient of dimer acid, thereby improving the abrasion resistance of dimer acid, and is suitable for being used as an abrasion resistant agent.

Examples 8 to 9

A dimer acid antiwear agent composition was prepared according to the method of example 1, except that the amount of dimer acid added in step (2) was varied, as shown in Table 4 below:

TABLE 4

	Dimer acid content
		Example 1	60wt％
Example 8	40wt％
		Example 9	80wt％

Example 10

A dimer acid antiwear agent composition was prepared in accordance with the method of example 1, except that, prior to step (2), the method further included subjecting the dimer acid obtained to a hydrofinishing treatment, wherein the reaction temperature was 150 ℃ and the reaction initiation H was₂The pressure is 2MPa, and the hydrogenation catalyst is Pd/Al₂O₃The catalyst accounts for 5 wt% of the content of the dimer acid, and the reaction time is 4 h. After the hydrogenation reaction, the content of dimer acid olefin is measured and analyzed by a liquid chromatograph and an infrared spectrometer, and the content of dimer acid olefin is measured to be 30%.

Examples 11 to 13

Dimer acid antiwear agent compositions were prepared according to the method of example 10, except that the reaction temperature, reaction pressure, catalyst type and content were changed, respectively, to obtain dimer acids with different olefin contents, as shown in table 5 below:

TABLE 5

Example 14

A dimer acid antiwear agent composition was prepared according to the method of example 1, except that decene was used as the built-up agent in step (2).

Comparative example 3

A dimer acid antiwear agent composition was prepared according to the method of example 1, except that decalin was used as the compounding agent in step (2).

Comparative example 4

A dimer acid antiwear agent composition was prepared according to the method of example 1, except that xylene was used as the built-up agent in step (2).

Test example

The dimer acid antiwear agent compositions of examples 1, 3-13 and comparative examples 3-4 were added to jet fuel No. 3, respectively, in such an amount that the concentration of dimer acid as the main agent was maintained at 20 mg/L. Lubricity evaluation experiments were carried out according to the lubricity measurement method listed in GB 6537, namely SH/T0687 aviation turbine fuel lubricity measurement method (ball column lubricity evaluator method). The apparatus used was an INTER Av BOC 100 model ball column lubricity tester, USA. GB 6537 requires that the diameter of the abrasion trace of military aviation fuel is not more than 0.65mm, and the diameter of the abrasion trace of civil aviation fuel is not more than 0.85 mm. The results are given in table 6 below:

TABLE 6

As can be seen from the analysis of Table 6 above, it can be seen from examples 1-3 that the difference in the raw materials affects the yield and structural distribution of dimer acid, and thus the antiwear properties of the antiwear agent. Preferably, the feedstock is selected from tall oil fatty acids.

As can be seen from examples 1 and 4 to 7, when the Si/Al ratio content in the catalyst is different, the catalytic activity of the catalyst is affected, and further the yield and the structural distribution of dimer acid are affected, so that the antiwear performance is changed. It can be seen that when the Si/Al ratio of the catalyst is 20-40: 1, the yield of the dimer acid is high, and the ratio of the monocyclic dimer acid to the catalyst is high.

It can be seen from examples 1, 8-9 that the dimer acid wear scar diameters differ when the amount of base compound in the dimer acid antiwear agent composition is different. Preferably, the effect is better when the content of the dimer acid as the main agent is 60 wt%.

It can be seen from examples 1 and 10-13 that, when dimer acid is further hydrorefined, the antiwear property is significantly improved compared with that of the dimer acid without hydrorefining, and the antiwear property is further improved with the decrease of olefin content. The reduction of the olefin content of the dimer acid can be seen, and the abrasion resistance is obviously improved.

As can be seen from example 1 and comparative examples 1-2, the dimer acid synthesized by using the catalyst of the invention is used in an antiwear agent, and the performance of the dimer acid is obviously superior to that of other catalysts. Therefore, the catalyst for synthesizing the dimer acid has an important effect on improving the anti-wear performance of the dimer acid anti-wear agent.

As can be seen from examples 1, 14 and comparative examples 3-4, dimer acid antiwear agents were prepared using different compounding agents, with an effect on the performance of the antiwear agent. Among them, tetrahydronaphthalene or decene is preferably used as the compounding agent.

It should be noted that the foregoing test examples were conducted while ensuring that the concentrations of the dimer acid base stock added to the fuel oil in the respective examples were the same, that is, the amounts of the raw materials consumed were different while ensuring that the concentrations of the dimer acid base stock were the same, due to the different conditions, for example, the yields of the dimer acid obtained using different catalysts, raw materials, and the like. Taking clay catalyst as an example, the yield of dimer acid is only 60.6 wt%, while the yield of dimer acid in the embodiment 1 of the present invention can reach 84.1 wt%, in order to ensure that the added concentration of dimer acid is the same, the amount of the antiwear agent composition used is at least 20 wt% more than that of the present invention, the obtained antiwear diameter is only 0.614mm, the antiwear effect is worse than that of the present invention, and more antiwear agent composition may be consumed in order to achieve the corresponding antiwear effect. Therefore, in fact, the antiwear agent composition disclosed by the invention is better in antiwear effect, has the beneficial effects of greatly saving raw materials and cost, and has a good industrial application prospect.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.