CN111349489B - Low-sulfur diesel lubricity improver and synthesis method and application thereof - Google Patents
Low-sulfur diesel lubricity improver and synthesis method and application thereof Download PDFInfo
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- CN111349489B CN111349489B CN201811574848.XA CN201811574848A CN111349489B CN 111349489 B CN111349489 B CN 111349489B CN 201811574848 A CN201811574848 A CN 201811574848A CN 111349489 B CN111349489 B CN 111349489B
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- sulfur diesel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
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- C10L2270/00—Specifically adapted fuels
- C10L2270/02—Specifically adapted fuels for internal combustion engines
- C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
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- Combustion & Propulsion (AREA)
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Abstract
The invention relates to a synthesis method of a low-sulfur diesel lubricity improver, which comprises the steps of feeding unsaturated monocarboxylic acid and tung oil biodiesel into a premixing tank according to a proportion, then feeding a mixed solution into a microchannel reactor, carrying out reaction at the temperature of 110-150 ℃, and carrying out reduced pressure distillation after the reaction is finished to obtain a lubricity improver product. In the microchannel reactor, unsaturated monocarboxylic acid is used for modifying tung oil biodiesel, and the prepared modifier is used for improving the lubricity of low-sulfur diesel oil, has the advantages of good low-temperature fluidity, good lubricity, low blending ratio, low acid value and the like, and can enable the low-sulfur diesel oil to meet the national V lubricity standard and the condensation point requirement after blending.
Description
Technical Field
The invention belongs to the technical field of biodiesel, and particularly relates to a low-sulfur diesel lubricity improver as well as a synthesis method and application thereof.
Background
With the widespread use of diesel engines, the consumption of diesel fuel is increasing year by year. However, the large consumption of diesel fuel inevitably leads to further aggravation of the emission of harmful substances from vehicles. Since emissions have a serious impact on the ecological environment, human health and economic development, governments in various countries have successively enacted strict emissions regulations, limiting the harmful emissions of diesel vehicles. With the implementation of national standard V of diesel oil, the sulfur content of the diesel oil is reduced to below 10ppm, and the desulfurized diesel oil is implemented in domestic refineries. At present, sulfur reduction technologies such as hydrotreating, hydrocracking and the like are adopted in China, so that the sulfur content of fuel is greatly reduced, and the content of polar compounds in diesel oil is too low, so that the lubricity of the diesel oil is greatly reduced, the phenomenon of abrasion and damage of a large number of diesel oil pumps is caused, and the service life of the diesel oil pumps is shortened. The problem of lubricity of diesel oil is the first to appear in northern Europe, early nineties, the first low-sulfur diesel oil produced in Sweden has a sulfur content of less than 10ppm, aromatic hydrocarbons of less than 5%, a second sulfur content of less than 50ppm, and aromatic hydrocarbons of less than 20%, and the fraction of the diesel oil is basically kerosene fraction (95% distillation range is not more than 285 ℃), so that the natural lubricity of the diesel oil is reduced. When this diesel fuel was marketed, there began to be approximately 70 light duty diesel vehicles with fuel injection pump wear problems. In the popularization and use of low-sulfur diesel oil in the United states, a large number of lubrication problems are reported, particularly in winter low-cloud-point diesel oil, and when the sulfur content is lower than 100ppm, the problem of abrasion of an oil injection pump is already caused under the dual effects of the two factors due to poor lubricity and low viscosity of oil products. Therefore, improving the lubricity of low-sulfur diesel is one of the key problems in solving the wide-range popularization of low-sulfur diesel.
At present, a plurality of organizations develop the research of directly using vegetable oil as the low-sulfur diesel anti-wear agent. CS275894, EP605857 disclose the use of natural oils and fats such as rapeseed oil, sunflower oil, castor oil, etc. as anti-wear agents for low sulphur diesel oil directly. Although the vegetable oil has the advantages of easily available raw materials, low price and the like, the vegetable oil has relatively poor using effect, and has the defects of high viscosity, high condensation point and the like, so the vegetable oil is difficult to industrially apply.
The latest research result shows that the lubricity can be greatly improved by adding the biodiesel into the low-sulfur diesel, and the additional value of the biodiesel can be obviously improved. However, the lubricating effect of biodiesel can only be achieved at a relatively high addition level, and the addition level is usually more than 0.8% (volume fraction) so as to reduce the wear scar diameter of low-sulfur diesel to less than 460 μm (the enhancing effect of biodiesel on the lubricity of low-sulfur diesel [ J ], [ petroleum refining and chemical industry ], [ 2005,36(7): 25-28), so that the economic efficiency of biodiesel as an additive is poor. In addition, the biodiesel contains a large amount of saturated fatty acid methyl ester, the condensation point is usually above-5 ℃, the use requirement of the low-sulfur diesel antiwear agent cannot be met, and the biodiesel cannot be suitable for cold regions. Therefore, the lubricity of the biodiesel can be improved by a molecular modification means, and the blending proportion and the product solidifying point of the biodiesel in low-sulfur diesel can be reduced.
CN1990835A discloses a preparation method of modified biodiesel capable of being used as a low-sulfur diesel antiwear agent, which greatly reduces the blending ratio, and the disclosed technical means is that biodiesel and polyalcohol perform ester exchange reaction or biodiesel and organic amine perform aminolysis reaction, thereby obtaining a modified biodiesel product. However, when the polyol is used as a raw material to perform ester exchange reaction, a polyester structure is easily formed, so that the condensation point of the product is too high, and the product performance cannot meet the requirement.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a low-sulfur diesel lubricity improver and a synthesis method and application thereof. In the microchannel reactor, unsaturated monocarboxylic acid is used for modifying tung oil biodiesel, and the prepared modifier is used for improving the lubricity of low-sulfur diesel oil, has the advantages of good low-temperature fluidity, good lubricity, low blending ratio, low acid value and the like, and can enable the low-sulfur diesel oil to meet the national V lubricity standard and the condensation point requirement after blending.
The synthesis method of the low-sulfur diesel lubricity improver provided by the invention comprises the following steps: respectively feeding unsaturated monocarboxylic acid and tung oil biodiesel into a premixing tank according to a certain proportion, then feeding the mixed solution into a microchannel reactor, reacting at the temperature of 110-150 ℃, and carrying out reduced pressure distillation after the reaction is finished to obtain the lubricity improver product.
In the present invention, the carbon number of the unsaturated monocarboxylic acid is preferably not less than 3, and preferably the unsaturated monocarboxylic acid has 4 to 8 carbon atoms, and for example, it may be one or more selected from crotonic acid, pentenoic acid, hexenoic acid, etc., and preferably one or more selected from 1-butenoic acid, 4-pentenoic acid, 3-pentenoic acid, 2-pentenoic acid, 5-hexenoic acid, 4-hexenoic acid, 3-hexenoic acid, 2-hexenoic acid, etc. The molar ratio of the unsaturated monocarboxylic acid to the tung oil biodiesel is controlled to be 0.5:1-3:1, and preferably 0.8:1-2: 1.
In the invention, the tung oil biodiesel is fatty acid lower alcohol ester generated by the ester exchange reaction of tung oil and lower alcohol, the carbon atom number of the lower alcohol is preferably not more than 4, such as methanol, ethanol, n-propanol, n-butanol and the like, namely the tung oil biodiesel can be at least one of tung oil methyl ester, tung oil ethyl ester, tung oil propyl ester, tung oil butyl ester and the like, and preferably the tung oil methyl ester. The production process of biodiesel is various, and most commonly, a catalyst is used for catalyzing ester exchange reaction, namely natural oil and low-carbon alcohol are subjected to alcoholysis to obtain fatty acid low-carbon alcohol ester and glycerol under the action of the catalyst. The tung oil biodiesel used in the invention can be prepared by adopting conventional preparation methods in the field, such as an acid catalysis method, an alkali catalysis method, an enzyme catalysis method, a supercritical method and the like.
In the invention, the microchannel reactor can adopt a commercially available or self-made microchannel reactor. The reactor is made of special glass, ceramics, polytetrafluoroethylene, stainless steel or alloy and the like, has a structure of a heart shape, a diamond shape, a rectangle shape and the like which can enhance the mixing of reactants, and has an inner diameter of 0.2-1 mm. The microchannel reactor comprises at least two feeding ports and a discharging port, and the number and the positions of the feeding ports can be changed according to reaction requirements.
In the invention, the mixed solution in the premixing tank is fed into the microchannel reactor through a metering pump, and the reaction is maintained at 110-150 ℃ for 0.5-2 h.
In the invention, the pressure of the reduced pressure distillation is 30-150Pa, preferably 65-120Pa, and the temperature is 180-220 ℃, preferably 195-205 ℃.
The low-sulfur diesel lubricity improver is synthesized by the method. The synthesized improver is prepared by modifying tung oil biodiesel by unsaturated monocarboxylic acid in a microchannel reactor, and has high product yield, acid value of 80-150mgKOH/g and condensation point of less than or equal to-20 ℃. The prepared lubricity improver has the advantages of low blending ratio, good lubricity, good low-temperature fluidity, low acid value and the like, and can enable low-sulfur diesel to meet national V lubricity standard and condensation point requirements after blending.
The lubricity improver for low-sulfur diesel oil provided by the invention is used for improving the lubricity of low-sulfur diesel oil, and when the usage amount is 80-250ppm, the corrected wear scar diameter (60 ℃) of the low-sulfur diesel oil is not more than 460 microns. The low-sulfur diesel oil refers to diesel oil with the sulfur content of less than 10ppm and the abrasive wear point diameter of more than 580 mu m.
Compared with the existing lubricity improver, the invention has the following beneficial effects:
(1) according to the invention, by utilizing molecular structure modification, a polar group of unsaturated monocarboxylic acid with a certain chain length is introduced into a tung oil biodiesel molecular chain and forms an aliphatic ring structure, so that a bilateral entanglement effect can be formed on an adsorption film, the entanglement density is effectively improved, a lubricating film is more compact, and the lubricity of low-sulfur diesel is greatly improved. Meanwhile, due to the introduction of an aliphatic ring structure, the intermolecular internal bonding effect is reduced, and the condensation point of the improver product can be reduced. The product performance of the improver prepared by the invention, such as the indexes of condensation point, flash point, metal content, low-temperature storage stability and the like, all meet the technical requirement of diesel antiwear agent (Q/SHCG 57-2014) of medium petrochemical industry.
(2) In a synthesis system, tung oil biodiesel and unsaturated monocarboxylic acid are incompatible two-phase reaction, and because the molecular weight of the tung oil biodiesel is larger, larger reaction steric hindrance exists, so that the reaction rate is reduced, the reaction temperature must be increased to promote the reaction, and the reaction temperature is usually higher than 200 ℃. Even if the product is prepared by adopting a conventional one-time feeding method in the presence of a polymerization inhibitor, free radical polymerization is easy to occur at such high temperature to form a macromolecular crosslinking structure, so that the product cannot be applied. And by adopting a dropwise feeding method, although the crosslinking problem can be solved to a certain extent, the product conversion rate is less than 90%. Therefore, the unsaturated monocarboxylic acid modified tung oil biodiesel is completed in the microchannel reactor, the cross-linking polymerization of the tung oil biodiesel can be avoided under the condition of no polymerization inhibitor, the conversion rate of the tung oil biodiesel is improved, the reaction temperature can be effectively reduced, the reaction time is shortened, and the low-temperature property of the product is improved.
(3) The product is a low-acid lubricity improver, has the characteristics of good lubricity, difficult emulsification, difficult precipitation at low temperature and the like, is particularly suitable for high-acid-value low-condensation diesel oil, cannot influence the acid value of the diesel oil, and avoids corrosion to a diesel engine.
(4) The product uses tung oil biodiesel as a main raw material, and widens the raw material source of the low-sulfur diesel improver. In addition, the invention has the characteristics of simple and convenient process, easily obtained raw materials, low cost, easy industrial production and the like.
Drawings
FIG. 1 is a flow diagram of one configuration of a microchannel reactor for use in the present invention;
wherein: the system comprises a 1-tung oil biodiesel storage tank, a 2-unsaturated monocarboxylic acid storage tank, a 3-premixing tank, a 4-heat conduction oil heating tank, a 5-oil bath tank, a 6-microchannel and a 7-product storage tank.
FIG. 2 is a gas chromatogram of a methyl ester feedstock of tung oil.
FIG. 3 is a gas chromatogram of the reaction product of example 1.
Detailed Description
The low sulfur diesel lubricity improvers of the present invention, methods of synthesis, and uses are further illustrated by the following examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
The synthesis process of the invention is shown in figure 1, the microchannel reactor comprises a metering pump, a premixing tank, a microchannel, an oil bath tank, a high-temperature oil pump and a heat-conducting oil heating tank, wherein the microchannel is arranged in the oil bath tank and is immersed in the heat-conducting oil; the heat conducting oil heating tank is communicated with the oil bath tank through a high-temperature oil pump and a heat conducting oil pipeline and is used for controlling the temperature of the heat conducting oil in the oil bath tank. Firstly, respectively feeding unsaturated monocarboxylic acid and tung oil biodiesel into a premixing tank in proportion by a metering pump, then feeding the mixed solution into a microchannel reactor, reacting at the temperature of 110-.
The acid value of the lubricity improver is measured according to the method GB/T7304, the condensation point is measured according to the method GB/T510, and the lubricity is measured according to the method SH/T0765 (lubricity refers to the diameter of the wear scar of low-sulfur diesel oil after the improver is added).
Detecting the content of conjugated octadecatrienoic acid ester containing conjugated double bonds in the tung oil biodiesel according to a gas chromatography, wherein the chromatographic analysis conditions are as follows: a FID detector; the size of a chromatographic column is 100 mm multiplied by 0.25mm multiplied by 0.20 mu m, and the temperature of a sample inlet is 260 ℃; the sample volume is 1 mu L; split-flow sample injection, split-flow ratio 100: 1; the temperature raising program is that the temperature is raised to 240 ℃ at a speed of 4 ℃/min and is kept for 4min after the temperature is raised to 140 ℃; the detector temperature was 260 ℃. Through detection, the content of the conjugated octadecatrienoic acid ester B = 70%.
Conversion rate of tung oil biodiesel A = (m)1-m2）/m1X 100%. Wherein m is1The feeding quality of the tung oil biodiesel is improved; m is2The quality of the tung oil biodiesel is separated after the reaction.
The conversion rate of carbon-carbon conjugated double bonds of the tung oil biodiesel = A/B × 100%.
Example 1
Preparing tung oil methyl ester: adding 800g of tung oil, 160g of methanol and 8g of potassium hydroxide into a 2L high-pressure reaction kettle, stirring for reaction at the temperature of 60 ℃ for 20min, standing for layering after the reaction is finished, separating out 76.2g of lower-layer glycerin product, washing the upper-layer glycerin product for 3 times by using hot water at the temperature of 50 ℃, and distilling the washed product for 2 hours at the temperature of 2000Pa and 60 ℃ to obtain the tung oil methyl ester biodiesel.
Feeding 4-pentenoic acid and tung oil methyl ester into a premixing tank according to the molar ratio of 1:1, and then feeding the mixture into a microchannel reactor through a metering pump, wherein the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. Through calculation, the conversion rate of reaction molecules (the conversion rate of carbon-carbon conjugated double bonds of methyl tung oil, the same applies below) is 95.1%. The detection shows that the acid value of the product is 132.7mgKOH/g, and the condensation point is-27.3 ℃. As can be seen from FIGS. 2 and 3, a new compound peak at an outflow time of 14.43min was observed, demonstrating the formation of the improver product.
Example 2
Feeding 4-pentenoic acid and tung oil methyl ester into a premixing tank according to a molar ratio of 0.5:1, and then feeding the mixture into a microchannel reactor through a metering pump, wherein the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 110 ℃, and the reaction time is 2 hours. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 88.5 percent, the acid value of the product is 125.0 mgKOH/g, and the condensation point is-24.2 ℃.
Example 3
Feeding 4-pentenoic acid and tung oil methyl ester into a premixing tank according to the molar ratio of 3:1, and then feeding the mixture into a microchannel reactor through a metering pump, wherein the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 150 ℃, and the reaction time is 0.5 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 96.8 percent, the acid value of the product is 128.8mgKOH/g, and the condensation point is-25.8 ℃.
Example 4
Feeding 4-pentenoic acid and tung oil methyl ester into a premixing tank according to the molar ratio of 1:1, and then feeding the mixture into a microchannel reactor through a metering pump, wherein the microchannel reactor is made of stainless steel and has a diamond structure, the inner diameter of the reactor is 1.0mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 95.8 percent, the acid value of the product is 125.7 mgKOH/g, and the condensation point is-25.5 ℃.
Example 5
Feeding 5-hexenoic acid and tung oil methyl ester into a premixing tank according to the molar ratio of 1:1, and then feeding the mixture into a microchannel reactor through a metering pump, wherein the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 94.0 percent, the acid value of the product is 128.6 mgKOH/g, and the condensation point is-28.7 ℃.
Example 6
1-butenoic acid and tung oil methyl ester are fed into a premixing tank according to the molar ratio of 1:1, and then are fed into a microchannel reactor through a metering pump, the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 96.6 percent, the acid value of the product is 137.7 mgKOH/g, and the condensation point is-25.9 ℃.
Example 7
Acrylic acid and tung oil methyl ester are fed into a premixing tank according to the molar ratio of 1:1, and then are fed into a microchannel reactor through a metering pump, the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 75.7 percent, the acid value of the product is 148.8mgKOH/g, and the condensation point is-20.6 ℃.
Example 8
1-octenoic acid and tung oil methyl ester are fed into a premixing tank according to the molar ratio of 1:1, and then are fed into a microchannel reactor through a metering pump, the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 81.1 percent, the acid value of the product is 122.8 mgKOH/g, and the condensation point is-30.6 ℃.
Example 9
Adding 800g of tung oil, 230g of ethanol and 8g of potassium hydroxide into a 2L high-pressure reaction kettle, stirring for reaction at the temperature of 60 ℃ for 20min, standing for layering after the reaction is finished, separating 74.8g of lower-layer glycerol product, washing the upper-layer product for 3 times by using hot water at the temperature of 50 ℃, and distilling the washed product for 2 hours at the temperature of 2000Pa and 60 ℃ to obtain the tung oil ethyl ester biodiesel.
Feeding 4-pentenoic acid and ethyl tung oil into a premixing tank according to the molar ratio of 1:1, and then feeding the mixture into a microchannel reactor through a metering pump, wherein the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 91.2 percent, the acid value of the product is 130.7 mgKOH/g, and the condensation point is-27.7 ℃.
Example 10
Adding 800g of tung oil, 320g of n-propanol and 8g of potassium hydroxide into a 2L high-pressure reaction kettle, stirring for reaction at the temperature of 60 ℃ for 20min, standing for layering after the reaction is finished, separating 72.4g of lower-layer glycerol product, washing the upper-layer glycerol product for 3 times by using 50 ℃ hot water, and distilling the washed product at the temperature of 2000Pa and 60 ℃ for 2h to obtain the tung oil propyl ester biodiesel.
Feeding 4-pentenoic acid and tung oil propyl ester into a premixing tank according to the molar ratio of 1:1, and then feeding the mixture into a microchannel reactor through a metering pump, wherein the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 88.1 percent, the acid value of the product is 128.9 mgKOH/g, and the condensation point is-28.0 ℃.
Example 11
Adding 800g of tung oil, 400g of n-butanol and 8g of potassium hydroxide into a 2L high-pressure reaction kettle, stirring for reaction at the temperature of 60 ℃ for 20min, standing for layering after the reaction is finished, separating 70.4g of lower-layer glycerin product, washing the upper-layer glycerin product for 3 times by using 50 ℃ hot water, and distilling the washed product for 2 hours at the temperature of 2000Pa and 60 ℃ to obtain the tung oil butyl ester biodiesel.
Feeding 4-pentenoic acid and butyl tung oil into a premixing tank according to the molar ratio of 1:1, and then feeding the mixture into a microchannel reactor through a metering pump, wherein the microchannel reactor is made of stainless steel and has a heart-shaped structure, the inner diameter of the reactor is 0.5mm, the temperature is controlled at 130 ℃, and the reaction time is 1 h. And after the reaction is finished, distilling for 2 hours under the conditions of the pressure of 65Pa and the temperature of 200 ℃ to obtain the low-sulfur diesel lubricity improver product. The conversion rate of reaction molecules is 87.2 percent, the acid value of the product is 126.6mgKOH/g, and the condensation point is-28.1 ℃.
Comparative example 1
The preparation process and the operation conditions are the same as those of the example 1, but the difference is that the common reactor is used, tung oil methyl ester biodiesel is gradually dripped, the dripping is completed within 2 hours, and the dripping speed is basically uniform. The reaction is difficult to carry out due to the low reaction temperature, the conversion rate of reaction molecules is less than 5 percent, and the modifier product cannot be synthesized.
Comparative example 2
The preparation process and the operation conditions are the same as those of the example 1, except that the conventional reactor is used, tung oil methyl ester biodiesel is gradually dripped, and the reaction temperature is increased to 220 ℃. Because the reaction temperature is too high, the tung oil methyl ester is polymerized to form a macromolecular crosslinking product, so that the conversion rate of the tung oil methyl ester is lower than 60 percent, the condensation point is too high to be-8 ℃, and the use standard specified in the technical requirement of diesel antiwear agents (Q/SHCG 57-2014) is not met.
Comparative example 3
The preparation process and operating conditions were the same as in example 1, except that other biodiesel, such as soybean oil biodiesel, cottonseed oil biodiesel, rapeseed oil biodiesel, castor oil biodiesel, corn oil biodiesel, peanut oil biodiesel, linseed oil biodiesel, etc., was used. Because the molecule of the biodiesel does not contain conjugated double bonds, the system does not react, and the product cannot be obtained.
Comparative example 4
The preparation process and the operation conditions are the same as those of the example 1, and the difference is that the unsaturated dicarboxylic acid is adopted to replace the unsaturated monocarboxylic acid, in particular 2-glutaconic acid, and the product has overlarge polarity and is incompatible with low-sulfur diesel oil, so that the product cannot be used as a low-sulfur diesel oil lubricity improver.
Test example 1
The low-sulfur diesel oil used in the test examples of the invention is hydrofined diesel oil with the sulfur content of less than 10ppm and the wear-leveling diameter of more than 580 μm, and the specific properties of the low-sulfur diesel oil are shown in Table 1.
TABLE 1 Main physical Properties of two low-sulfur diesel fuels
The lubricity improver prepared by the invention is added into the low-sulfur diesel oil for product performance test. The test results are shown in tables 2 and 3.
TABLE 2
As can be seen from Table 2, the lubricating effect of the directly adopted tung oil biodiesel on low-sulfur diesel oil is poor, when 800ppm of the lubricating agent is added, the lubricating property of the low-sulfur diesel oil does not meet the lubricating property requirement of national V diesel oil, and the improver is separated out at the temperature of-20 ℃, so that the addition amount is high. The lubricity of the product modified by the method is obviously improved, when the addition amount is reduced to 130ppm, the blended low-sulfur diesel can meet the requirement that the abrasive wear pattern diameter is not more than 460 mu m, and no precipitation is generated at-20 ℃. The prepared lubricity improver has obvious lubricating effect, and is low in blending ratio and condensation point.
TABLE 3
As can be seen from Table 3, the direct use of tung oil biodiesel as a lubricity improver had poor lubricating effect on low-sulfur diesel, and when 800ppm was added, the lubricity of the low-sulfur diesel did not meet the lubricity requirements of national V diesel, and the improver precipitated at-30 ℃ did not meet the use requirements. The lubricity improver synthesized by the method provided by the invention can obviously improve the lubricity of low-sulfur diesel, when the addition amount is reduced to 180ppm, the blended low-sulfur diesel can meet the requirement of national V diesel lubricity (the wear-spot diameter is no more than 460 μm), and particularly, no improver is separated out after the diesel is blended with the low-sulfur diesel at the low temperature of-30 ℃, so that the quality of the diesel is not influenced. The novel lubricity modifier prepared by the invention has obvious lubricating effect, low blending ratio and low condensation point.
Claims (11)
1. A synthetic method of a low-sulfur diesel lubricity improver is characterized by comprising the following steps: unsaturated monocarboxylic acid and tung oil biodiesel are fed into a premixing tank according to a proportion, then the mixed solution is fed into a microchannel reactor for reaction at the temperature of 110-; the unsaturated monocarboxylic acid is unsaturated monoalkenoic acid with 4-8 carbon atoms; the tung oil biodiesel is fatty acid low-carbon alcohol ester generated by the ester exchange reaction of tung oil and low-carbon alcohol, and the carbon atom number of the low-carbon alcohol is not more than 4; the molar ratio of the unsaturated monocarboxylic acid to the tung oil biodiesel is 0.5:1-3: 1; the reduced pressure distillation pressure is 30-150Pa, and the temperature is 180-220 ℃.
2. The method of claim 1, wherein: the unsaturated monocarboxylic acid is one or more of butenoic acid, pentenoic acid and hexenoic acid.
3. The method of claim 2, wherein: the unsaturated monocarboxylic acid is one or more of 1-butenoic acid, 4-pentenoic acid, 3-pentenoic acid, 2-pentenoic acid, 5-hexenoic acid, 4-hexenoic acid, 3-hexenoic acid and 2-hexenoic acid.
4. The method of claim 1, wherein: the molar ratio of the unsaturated monocarboxylic acid to the tung oil biodiesel is 0.8:1-2: 1.
5. The method of claim 1, wherein: the tung oil biodiesel is at least one of tung oil methyl ester, tung oil ethyl ester, tung oil propyl ester and tung oil butyl ester.
6. The method of claim 1, wherein: the microchannel reactor is made of special glass, ceramics, polytetrafluoroethylene, stainless steel or alloy, and has a heart-shaped, rhombic or rectangular structure, and the inner diameter of the reactor is 0.2-1 mm.
7. The method of claim 1, wherein: the mixed liquid in the premixing tank is sent into a micro-channel reactor through a metering pump, and reacts for 0.5-2h at the temperature of 110-150 ℃.
8. The method of claim 1, wherein: the reduced pressure distillation pressure is 65-120 Pa; the temperature was 195-.
9. A low sulfur diesel lubricity improver characterized by being synthesized by the method of any one of claims 1 to 8.
10. The use of a low sulfur diesel lubricity improver as claimed in claim 9 wherein: used for improving the lubricity of low-sulfur diesel oil, and when the dosage is 80-250ppm, the corrected wear scar diameter of the low-sulfur diesel oil is not more than 460 mu m.
11. Use according to claim 10, characterized in that: the low-sulfur diesel oil is diesel oil with the sulfur content less than 10ppm and the abrasive wear point diameter more than 580 mu m.
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Effective date of registration: 20231007 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |