A preparation method of naphthenate detergent

Abstract

The present invention discloses a preparation method of a naphthenate detergent, comprising the following steps: (1) Preparation of rare earth naphthenate: strong acid is used as an analytical solution to obtain soluble rare earth. Naphthenic acid, water and an alkali solution are added to a reaction kettle in proportion, and stirring and heating are carried out for saponification reaction to obtain a saponified solution. The soluble rare earth solution is added dropwise to the saponified solution, and after the addition is completed, a metathesis reaction is carried out, and pure rare earth naphthenate is obtained by washing with water to remove salt; (2) Preparation of a high-base naphthenate detergent: a phosphite stabilizer, n-butanol, neutral oil, an organic solvent and rare earth naphthenate are added to a reaction kettle for carbonation reaction to obtain a high-base rare earth naphthenate. The polyisobutenylamine and the high-base rare earth naphthenate are mixed at a ratio of 1-3:7-9 to obtain a naphthenate detergent. The rare earth naphthenate detergent obtained by the method of the present invention has the advantages of high detergency and dispersibility, strong neutralization effect, high colloidal stability, and reduction of CO and NO × emissions in automobile exhaust gas.

Description

Technical Field

[0001] The invention relates to the field of chemical industry, and in particular to a method for preparing a naphthenate detergent. Background Art

[0002] Metal detergent is one of the main additives in internal combustion engine oil. Through solubilization, dispersion and neutralization in internal combustion engine oil, it can inhibit the formation of carbon deposits, varnish and sludge in oil products together with other additives to ensure the normal operation of the engine. Naphthenate is a type of detergent that appeared earlier in history. The technology of trial-producing calcium and magnesium naphthenate salt series products using naphthenic acid obtained from lubricating oil fractions as raw materials is becoming increasingly mature. Rare earth is called the "treasure house" of new materials. It has the characteristics of purifying metals, high temperature resistance and high stability, but it is rarely used in detergents. The following are currently searched:

[0003] The isooctanoic acid rare earth diesel detergent is mainly obtained by reacting isooctanoic acid with rare earth nitrate after saponification of isooctanoic acid and sodium hydroxide. The detergent obtained by this disclosed method has the function of removing 75% of sediment, reducing CO emissions in automobile exhaust by 49.4%, and NO × The emission of diesel fuel was reduced by 34.2%. However, the preparation process and cost of isooctanoic acid are relatively high, so although isooctanoic acid rare earth diesel detergent has a good cleaning and dispersing effect, it has not been promoted and applied yet.

[0004] CN200610098259.X discloses a method for preparing a multifunctional diesel detergent. Adding alkyl rare earth to the detergent can improve the cleaning and dispersing effect of the detergent.

[0005] CN201710427536.5 discloses a composite diesel energy-saving detergent and a preparation method thereof, which uses organic acid rare earth as raw material. Organic acid rare earth is an acidic substance used as a detergent and cannot neutralize sulfur dioxide and sulfur trioxide generated by incomplete combustion of sulfur in an internal combustion engine. The acidic substances will corrode the metal surface, causing the internal combustion engine to function less well and shorten its service life.

[0006] The method of the present invention uses rare earth naphthenate to prepare detergent. First, the high-alkalinity rare earth naphthenate detergent can neutralize the acidic substances generated by incomplete combustion of gasoline. Second, rare earth naphthenate has the characteristics of metal purification, high temperature resistance, high stability, etc., and can be used as a detergent to effectively purify the sludge and paint film in the internal combustion engine, and has the characteristics of good cleaning and dispersibility. Third, rare earth naphthenate can reduce CO and NO in automobile exhaust. × emissions; fourth, adding phosphite stabilizers to improve the stability of rare earth cyclopentaneate colloids, extend their storage time, and improve their service life and use effect.

[0007] The information disclosed in this background section is only intended to enhance the overall understanding of the background of the present invention and should not be regarded as an admission or any form of suggestion that this information constitutes prior art known to those of ordinary skill in the art. Summary of the Invention

[0008] The object of the present invention is to provide a preparation method of naphthenate detergent, which has a high base number, can neutralize acidic substances generated by gasoline combustion, avoid corrosion of the metal surface of the fuel tank, effectively purify sludge and lacquer film in the internal combustion engine, has good detergency and dispersibility, and reduces CO and NO in automobile exhaust × emissions.

[0009] To achieve the above object, the present invention provides a preparation method of naphthenate detergent, which is characterized by including the following steps:

[0010] (1) Preparation of rare earth naphthenate: Strong acid is used as an analytical solution to obtain soluble rare earth. Naphthenic acid, water, and alkali solution are added to the reaction kettle in proportion, stirred and heated for saponification reaction to obtain a saponified solution. The soluble rare earth solution is added dropwise to the saponified solution. After the addition is completed, a metathesis reaction is carried out, and pure rare earth naphthenate is obtained by washing and desalting.

[0011] (2) Preparation of high-base-number naphthenate detergent: Phosphite stabilizer, methanol, n-butanol, neutral oil, organic solvent, and rare earth naphthenate are added to the reaction kettle, stirred and heated to obtain a mixed solution. CO is introduced into the mixed solution 2 for carbonation reaction to obtain high-base-number rare earth naphthenate. Polyisobutenylamine and high-base-number rare earth naphthenate are mixed in a ratio of 1-3:7-9 to obtain naphthenate detergent.

[0012] Preferably, in the above technical solution, the method for obtaining soluble rare earth in step (1) is to stir or soak the rare earth mixture with strong acid as an analytical solution for 3-4 h, and remove the precipitate after standing; wherein,

[0013] the strong acid refers to one or more of nitric acid and hydrochloric acid.

[0014] Preferably, in the above technical solution, the ratio of naphthenic acid, water, and alkali solution in step (1) is 1.5-2.5:0.7-1.3:1.5-2.5; wherein,

[0015] the alkali solution is one or a mixture of several of sodium hydroxide, calcium hydroxide, and potassium hydroxide.

[0016] Preferably, in the above technical solution, the temperature of the saponification reaction in step (1) is 90-100 °C.

[0017] Preferably, in the above technical solution, the temperature of the metathesis reaction in step (1) is maintained at 90-100 °C.

[0018] Preferably, in the above technical solution, the component ratio of the naphthenate detergent in step (2) is 15-35 g of phosphite stabilizer, 15-25 g of methanol, 20-30 g of n-butanol, 30-45 g of neutral oil, 200-300 ml of organic solvent, and 68-110 g of rare earth naphthenate

[0019] Preferably, in the above technical solution, the organic solvent in step (2) is one or more of xylene, gasoline, and octane.

[0020] Preferably, in the above technical solution, the phosphite stabilizer in step (2) includes one or more of triphenyl phosphite (TPP), triphenyl phosphite, and triethyl phosphite.

[0021] Preferably, in the above technical solution, the temperature for stirring and heating in step (2) is 50-70 °C.

[0022] Preferably, in the above technical solution, the ventilation rate of CO2 introduced in step (2) is 50-100 ml / min.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) Due to the characteristics of the rare earth naphthenate such as its purification effect on metals, high temperature resistance, and high stability, when used as a detergent, it can effectively purify the sludge and paint film in the internal combustion engine and has good detergency and dispersibility.

[0025] (2) The rare earth naphthenate can reduce the emissions of CO and NO in automobile exhaust. × emissions.

[0026] (3) The high-base rare earth naphthenate detergent can neutralize the acidic substances generated by incomplete gasoline combustion.

[0027] (4) Adding a phosphite stabilizer can improve the colloidal stability of the rare earth naphthenate, extend its storage time, and improve its service life and usage effect. Specific Embodiments

[0028] The following will describe the specific embodiments of the present invention in detail in conjunction with specific examples, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0029] Example 1

[0030] A preparation method of a naphthenate detergent, comprising the following steps:

[0031] (1) Preparation of rare earth naphthenate: Add HCl and rare earth mixture into a reaction kettle equipped with a stirrer, stir and soak for 3 h, remove the precipitate after standing, obtain soluble rare earth, add 150 g of naphthenic acid, 70 g of water, and 150 g of potassium hydroxide into the reaction kettle, stir and heat to 90 °C for saponification reaction to obtain a saponified solution. Dropwise add the soluble rare earth solution into the saponified solution, and after dropping, carry out a metathesis reaction at a temperature maintained at 90 °C, and obtain pure rare earth naphthenate by washing and desalting;

[0032] (2) Preparation of overbased naphthenate detergent: Add 15 g of phosphite stabilizer, 35 g of n-butanol, 30 g of neutral oil, 200 ml of 150 solvent oil, and 68 g of rare earth naphthenate into a three-necked reaction kettle equipped with a stirrer, a ventilation duct, and a thermometer, stir and heat up to 50 °C to obtain a mixed solution, and introduce CO into the mixed solution at a ventilation rate of 50 ml / min 2 After carrying out the carbonation reaction, obtain overbased rare earth naphthenate with a base number of 306 mg KOH / g, and mix polyisobutenylamine and overbased rare earth naphthenate at a ratio of 1:9 to obtain a naphthenate detergent.

[0033] Example 2

[0034] A preparation method of a naphthenate detergent, comprising the following steps:

[0035] (1) Preparation of rare earth naphthenate: Add HCl and rare earth mixture into a reaction kettle equipped with a stirrer, stir and soak for 3 h, remove the precipitate after standing, obtain soluble rare earth, add 200 g of naphthenic acid, 104 g of water, and 200 g of sodium hydroxide into the reaction kettle, stir and heat to 95 °C for saponification reaction to obtain a saponified solution. Dropwise add the soluble rare earth solution into the saponified solution, and after dropping, carry out a metathesis reaction at a temperature maintained at 90 °C, and obtain pure rare earth naphthenate by washing and desalting;

[0036] (2) Preparation of overbased naphthenate detergent: Add 25 g of triphenyl phosphite stabilizer, 45 g of n-butanol, 35 g of neutral oil, 150 ml of octane, 100 ml of gasoline, and 80 g of rare earth naphthenate into a three-necked reaction kettle equipped with a stirrer, a ventilation duct, and a thermometer, stir and heat up to 60 °C to obtain a mixed solution, and introduce CO into the mixed solution at a ventilation rate of 70 ml / min 2 After carrying out the carbonation reaction, obtain overbased rare earth naphthenate with a base number of 311 mg KOH / g, and mix polyisobutenylamine and overbased rare earth naphthenate at a ratio of 2:8 to obtain a naphthenate detergent.

[0037] Example 3

[0038] A preparation method of a naphthenate detergent, comprising the following steps:

[0039] (1) Preparation of rare earth naphthenate: Add HNO 3 and the rare earth mixture into a reaction kettle equipped with a stirrer, stir and soak for 4 h, remove the precipitate after standing, obtain soluble rare earth. Add 137.5 g of naphthenic acid, 71.5 g of water, and 137.5 g of lye into the reaction kettle, stir and heat to 100 °C for saponification reaction to obtain a saponified solution. Dropwise add the soluble rare earth solution into the saponified solution, and after dropping, carry out a metathesis reaction at a temperature maintained at 100 °C, and obtain pure rare earth naphthenate through water washing and desalting;

[0040] (2) Preparation of overbased naphthenate detergent: Add 35 g of triethyl phosphite stabilizer, 55 g of n-butanol, 45 g of neutral oil, 300 ml of gasoline, and 110 g of rare earth naphthenate into a three-necked reaction kettle equipped with a stirrer, a ventilation duct, and a thermometer, stir and heat up to 70 °C to obtain a mixed solution. Pass CO 2 into the mixed solution at a ventilation rate of 100 ml / min for carbonation reaction, and obtain overbased rare earth naphthenate with a base number of 321 mg KOH / g. Mix polyisobutenylamine and overbased rare earth naphthenate at a ratio of 3:7 to obtain a naphthenate detergent.

[0041] Example 4

[0042] Respectively add the detergent products prepared in Examples 1, 2, and 3 into unleaded gasoline to prepare gasoline products Product 1, Product 2, and Product 3 and a blank gasoline product without adding a detergent, where the detergent accounts for 4% of the total mass of the gasoline product.

[0043] Carry out a detergency and dispersibility evaluation test on Product 1, Product 2, and Product 3 respectively, and the results are shown in Table 1.

[0044] Table 1 Results of detergency and dispersibility evaluation test

[0045] Evaluation Items Coke Yield / mg Lacquer Yield / mg Test Method SH / T0300-92 SH / T0300-92 Blank (without detergent additive) 25.6 15.7 Product 1 15.6 8.2 Product 2 14.2 7.4 Product 3 13.4 6.8

[0046] As shown in Table 1, when the detergent products prepared in Examples 1, 2, and 3 of the present invention are added to gasoline, compared with the blank product of gasoline without adding a detergent, the coking amount on the fuel tank wall and parts is reduced by 63.06%, and the lacquering amount is reduced by 90.24%. It shows that the rare earth naphthenate detergent obtained by the method of the present invention has the ability to adsorb particulate soot and carbon particles, avoid the aggregation and precipitation of particulate soot and carbon particles on the metal surface, thereby reducing the generation of coking amount and lacquering amount on the fuel tank wall and parts.

[0047] Example 5

[0048] Separate 1L of blank unleaded gasoline and 1L of unleaded gasoline with rare earth naphthenate detergent accounting for 1%, 2%, 3%, 4%, and 5% of the total mass of the gasoline product. When burning at an idle speed of 1500 r / min in a Mitsubishi single-cylinder gasoline engine, use a German-made testo350-XL flue gas analyzer to detect hydrocarbons (HC), CO, and NO x in the exhaust gas generated by the engine. The results are shown in Table 2.

[0049] Table 2 CO and NO in the exhaust gas generated by the engine x Situation

[0050] Detergent Concentration Blank 1％ 2％ 3％ 4％ 5％ <![CDATA[HC / 10 -6 > 90 5.8 5.5 4.3 4 4 CO / % 0.5 0.06 0.05 0.03 0.02 0.02 <![CDATA[NO x / 10 -6 > 700 4 3.6 3.1 3 2.8

[0051] As shown in Table 2, for gasoline with a higher concentration of the rare earth naphthenate detergent of the present invention, the concentrations of HC, CO, and NO in the exhaust gas generated by the engine x are lower. And when the rare earth naphthenate detergent accounts for 4% of the total mass of the gasoline product, the HC concentration in the exhaust gas drops to 4×10 -6 , the CO concentration drops to 0.02%, and NO x concentration drops to 3×10 -6 , indicating that the rare earth naphthenate detergent can improve the degree of complete combustion of the fuel and reduce the emissions of HC, CO, and NO x , thereby achieving the goal of reducing the emissions of automotive exhaust pollutants.

[0052] The quality inspection of the self-made gasoline naphthenate detergent product is as shown in Table 3 according to GB 19592-2019.

[0053] Table 3 Inspection Report of Petrochemical Products of Self-made Products (N o .202104377)

[0054]

[0055] As shown in Table 3, in the inspection of petrochemical products of the self-made gasoline detergent obtained by the present invention, the detection data of each detection item are better than the quality standards of vehicle gasoline detergents required by GB 19592-2019, indicating that the self-made gasoline detergent obtained by the present invention meets the national standards for vehicle gasoline detergents in China and can be mass-produced and put on the market.

[0056] Comparative Example 1

[0057] Step (1) is the same as that in Example 1; the difference is that,

[0058] (2) Preparation of overbased naphthenate: Add 35 g of n-butanol, 30 g of neutral oil, 200 ml of 150 solvent oil, and 68 g of rare earth naphthenate into a three-necked reaction kettle equipped with a stirrer, a ventilation duct, and a thermometer. Stir and heat up to 50 °C to obtain a mixed solution. Pass CO into the mixed solution at a ventilation rate of 50 ml / min 2 After the carbonation reaction, an overbased rare earth naphthenate with a base number of 301 mg KOH / g is obtained. Mix polyisobutenylamine and the overbased rare earth naphthenate in a ratio of 1:9 to obtain a naphthenate detergent.

[0059] Comparative Example 2

[0060] Step (1) is the same as that in Example 1; the difference lies in that

[0061] (2) Preparation of overbased naphthenate: Add 15 g of zinc stearate stabilizer, 15 g of methanol, 20 g of n-butanol, 30 g of neutral oil, 100 ml of benzene, 100 ml of xylene, and 68 g of rare earth naphthenate into a three-necked reaction kettle equipped with a stirrer, a ventilation duct, and a thermometer. Stir and heat up to 50 °C to obtain a mixed solution. Pass CO into the mixed solution at a ventilation rate of 40 ml / min 2 After the carbonation reaction, a medium-based rare earth naphthenate with a base number of 278 mg KOH / g is obtained. Mix polyisobutenylamine and the medium-based rare earth naphthenate in a ratio of 1:9 to obtain a naphthenate detergent, and mix polyisobutenylamine and the overbased naphthenate in a ratio of 1:9 to obtain a naphthenate detergent.

[0062] Detect the colloidal stability of the overbased naphthenates obtained in Example 1 and Comparative Examples 1-2. The results are shown in Table 4.

[0063] Table 4 Colloidal stability of naphthenates obtained in Example 1 and Comparative Examples 1-2

[0064]

[0065]

[0066] As shown in Table 4, by using a phosphite stabilizer as the stabilizer of the detergent in the method of the present invention, compared with Comparative Examples 1 and 2, both the storage stability and the water stability in the colloidal stability of the rare earth naphthenate are below 1%, indicating that the phosphite stabilizer can significantly improve the colloidal stability of the rare earth naphthenate compared with not adding a stabilizer and using a zinc stearate stabilizer.

[0067] Comparative Example 3

[0068] The self-made gasoline detergent of the present invention was subjected to a simulated bench test (the results are shown in Table 5) and a gasoline engine exhaust emission test (the results are shown in Table 6) with the 3M brand PN7029 detergent and the ChePu brand CP525-1 detergent on the market. This simulated bench test was carried out using an L-2 self-controlled gasoline engine produced by Lanzhou Weike Petrochemical Instrument Co., Ltd.; this gasoline engine exhaust emission test was carried out when a Mitsubishi single-cylinder gasoline engine was burning at an idle speed of 1500 r / min, and a testo 350-XL type flue gas analyzer produced in Germany was used to detect the concentrations of hydrocarbons (HC), CO, and NO in the exhaust gas generated by the engine. In the tests conducted, the detergent accounted for 4% of the total mass of the gasoline product. x The concentration was detected, where the detergent accounted for 4% of the total mass of the gasoline product in the tests conducted.

[0069] Detergent dispersion effect = (Δt 1 -Δt 0 ) / Δt 1 , where

[0070] Δt 1 = non-additive precipitation amount + additive precipitation amount

[0071] Δt 0 = blank non-additive precipitation amount + blank additive precipitation amount

[0072] Table 5 Comparison of the effects of the self-made gasoline detergent of the present invention with the 3M brand PN7029 and the ChePu brand CP525-1

[0073]

[0074] As shown in Table 5, the detergent dispersion effect of the self-made gasoline detergent obtained by using the present invention reached 97.94%. Compared with the detergent dispersion effect of 60.56% of the 3M brand PN7029 detergent and 61.45% of the ChePu brand CP525-1 detergent existing on the market, the detergent dispersion effect of the rare earth naphthenate detergent of the present invention increased by about 35%.

[0075] Table 6 Comparison of the concentrations of HC, CO, and NO in the engine exhaust x Concentration

[0076]

[0077] As shown in Table 6, during the combustion process of adding the self-made gasoline detergent obtained by using the present invention to gasoline, the concentrations of HC, CO, and NO in the exhaust gas decreased significantly. Compared with gasoline added with the M brand PN7029 detergent and the ChePu brand CP525-1 detergent on the market, although during the combustion process of gasoline added with the detergents on the market, the HC, CO, and NO x in the exhaust gas xThe concentration has decreased, but the decrease amplitude is not as large as that of the detergent obtained in the present invention, indicating that the detergent obtained in the present invention can more effectively promote the combustion of gasoline, thereby reducing the generation of HC, CO, and NO during the combustion of gasoline. x .

[0078] From the above, it can be seen that the detergent obtained by preparing the high-base rare earth naphthenate in the present invention has strong detergency, good detergency and dispersibility for engine carbon deposits and sludge, reduces the drivability and power decline of engine parts caused by carbon deposits and sludge, effectively improves the use effect and service life of automobile engines, and reduces the engine loss rate and scrapping rate; adding gasoline containing the detergent of the present invention can promote the full combustion of gasoline, reduce the generation of harmful gases CO and NO in the exhaust gas. x , and at the same time reduce the content of HC in the exhaust gas, thereby reducing the input amount of harmful gases in the atmospheric environment and reducing air pollution; adding gasoline containing the detergent of the present invention can burn more fully. When the car travels the same mileage, it consumes less fuel, thereby reducing the CO 2 emission will also be relatively less, reducing the input amount of CO 2 in the atmospheric environment.

[0079] The foregoing description of specific exemplary embodiments of the invention has been presented for purposes of illustration and example. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is apparent that many modifications and variations are possible in light of the above teaching. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the invention and its practical applications, so that those skilled in the art can implement and utilize various different exemplary embodiments of the invention, as well as various different selections and modifications. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A preparation method of naphthenate detergent, characterized in that, the method comprises the following steps: S1, preparation of rare earth naphthenate: strong acid is used as an analytical solution to obtain soluble rare earth. Naphthenic acid, water, and alkali solution are added to a reaction kettle in proportion, stirred and heated for saponification reaction to obtain a saponified solution. The soluble rare earth solution is added dropwise to the saponified solution. After the addition is completed, a metathesis reaction is carried out, and pure rare earth naphthenate is obtained by washing with water to remove salts; the mass ratio of naphthenic acid, water, and alkali solution in S1 is 1.5 - 2.5:0.7 - 1.3:1.5 - 2.5; wherein, the alkali solution is one or a mixture of sodium hydroxide, calcium hydroxide, and potassium hydroxide; S2. Preparation of overbased naphthenate: Add phosphite stabilizer, n-butanol, neutral oil, organic solvent, and rare earth naphthenate into a reaction kettle, stir and heat up to obtain a mixed solution, and introduce CO into the mixed solution. 2 After carbonation reaction, overbased rare earth naphthenate is obtained. Mix polyisobutenylamine and overbased rare earth naphthenate at a ratio of 1-3:7-9 to obtain a naphthenate detergent; The component ratio of the overbased naphthenate described in S2 is 15-35 g of phosphite stabilizer, 35-55 g of n-butanol, 30-45 g of neutral oil, 200-300 ml of organic solvent, and 68-110 g of rare earth naphthenate; The phosphite stabilizer described in S2 includes one or more of trialkyl phosphite, triphenyl phosphite, and triethyl phosphite.

2. The preparation method of naphthenate detergent according to claim 1, characterized in that, the method for obtaining soluble rare earth in S1 is that strong acid is used as an analytical solution to stir or oscillate and soak the rare earth mixture for 3 - 4 h, and the precipitate is removed after standing; wherein, the strong acid refers to one or a mixture of nitric acid and hydrochloric acid.

3. The preparation method of naphthenate detergent according to claim 1, characterized in that, the temperature of the saponification reaction in S1 is 90 - 100 °C.

4. The preparation method of naphthenate detergent according to claim 1, characterized in that, the temperature of the metathesis reaction in S1 is maintained at 90 - 100 °C.

5. The preparation method of naphthenate detergent according to claim 1, characterized in that, the organic solvent in S2 includes one or a mixture of 150 solvent oil, gasoline, and octane.

6. The preparation method of naphthenate detergent according to claim 1, characterized in that, the temperature of stirring and heating in S2 is 50 - 70 °C.

7. The preparation method of naphthenate detergent according to claim 1, characterized in that, The CO introduced in S2 2 has an aeration rate of 50 - 100 ml / min.

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