JPH0546876B2 - - Google Patents

Description

[Detailed description of the invention]

[Prior Art] In recent years, petroleum middle distillate oils such as kerosene, light oil, and A-heavy oil are under pressure in quantity. As a countermeasure to this problem, the end point of atmospheric distillation is made higher than before.
So-called deep drawing has been used to improve the yield of petroleum middle distillates. For this reason, light oil and A-heavy oil tend to be heavier than before, and as a result, the low-temperature fluidity of these petroleum middle distillate oils has deteriorated. In other words, when heavy light oil, A heavy oil, etc. are exposed to low temperatures in winter or in cold regions, the wax-like substances contained therein precipitate, clogging the filter in the diesel engine's fuel piping system and causing damage to the engine. Problems arise such as problems with starting, etc., and the fuel oil itself becomes semi-solid or solid, losing fluidity and clogging the oil pipe. Straight-run light oil made heavier by deep drawing during atmospheric distillation,
In order to improve the low-temperature fluidity of heavy oil A and the like, various fluidity improvers have been used so far, and many improvers have been reported. Fluidity improvers that have been developed so far include, for example, ethylene-vinyl acetate copolymer, ethylene-(meth)
Acrylate copolymers, branched polyethylene, halogenated polyalkylenes, alkyl (meth)acrylate polymers, condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of alkenylsuccinic acids,
Examples include aliphatic dicarboxylic acid amides. [Problem to be solved by the invention] However, recently, petroleum middle distillate oil has become increasingly scarce, so heavy gas oil and vacuum gas oil, which have rarely been used as base materials for gas oil and A-heavy oil, have become increasingly scarce. , light oil using cracked light oil, etc.
Heavy oil production has begun. The composition of such light oils and A heavy oils is quite different from that of conventional straight-run oils, and conventional fluidity improvers do not exhibit good fluidity for these oils. Therefore, improvement is desired. [Means for solving the problem] Under these circumstances, the inventors of the present invention have conducted intensive research and have found that not only conventional straight-run gas oil and A heavy oil, but also heavy gas oil and vacuum gas oil can be cracked. The present invention was completed by discovering a compound that can impart good low-temperature fluidity to light oil mixed with light oil and heavy oil A. That is, the present invention provides the following (a) to (d) (a) α-olefin having 20 to 60 carbon atoms, maleic anhydride, and dialkyl maleate (provided that the alkyl group has 1 to 5 carbon atoms); (b) α-olefin having 20 to 60 carbon atoms and dialkyl maleate (however, the number of carbon atoms in the alkyl group is 1 to 50);
5) with a number average degree of polymerization of 2 to 50; (c) the compound of (a) above or α- having 20 to 60 carbon atoms;
A hydrolyzate or partial hydrolyzate of a copolymer of olefin and maleic anhydride with a number average degree of polymerization of 2 to 50, or a light metal salt thereof; (d) α-olefin having 20 to 60 carbon atoms and anhydride; A copolymer with maleic acid with a number average degree of polymerization of 2 to 2.
50 partially alkyl esterified products (however,
At least one compound selected from the group consisting of an alkyl group having 1 to 5 carbon atoms), a light metal salt thereof, or a hydrolyzate or partial hydrolyzate of a partial alkyl ester thereof, or a light metal salt thereof. The present invention provides fuel oil additives. Compound (a) used in the present invention can be produced as follows. That is, the number of carbon
A copolymer of 20 to 60 α-olefin, maleic anhydride and dialkyl maleate can be prepared by a known method,
For example, it is produced by reacting the above three types of compounds in the presence of an appropriate radical initiator without a solvent or using an appropriate solvent such as benzene, toluene, xylene, etc. at a temperature of 60 to 200°C for 1 to 20 hours. be done. The molar ratio of α-olefin and maleic anhydride used may be in the range of 0.5 to 1:1 to 0.5, preferably in the range of 0.8 to 1:1 to 0.8. Examples of α-olefins having 20 to 60 carbon atoms include 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, 1-octacosene,
Carbon number 20~ obtained by distilling α-olefin obtained by low polymerization of ethylene using a Ziegler type catalyst
Examples include α-olefin having a carbon number distribution of 28 and α-olefin having a carbon number of 30 or more and substantially 60 or less. These can be used alone or in combination. Furthermore, internal olefins and branched olefins may be included within a range that does not impair the effects of the present invention. Further, the copolymer of compound (b), an α-olefin having 20 to 60 carbon atoms, and dialkyl maleate can also be easily produced according to the above production method.
In addition, by reacting a copolymer of α-olefin and maleic anhydride obtained according to the above method with an equivalent or more amount of a monohydric alcohol having 1 to 5 carbon atoms, α-olefin and maleic anhydride can be mixed. It is possible to produce a product having the same structure as a dialkyl copolymer. 1 that can be used in this case
Examples of the alcohol include methyl alcohol, ethyl alcohol, 1-propanol, isopropyl alcohol, n-butyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, sec-n-amyl alcohol, sec-iso-
Examples include amyl alcohol, tert-amyl alcohol, and the like. The copolymer of α-olefin and maleic anhydride and these monohydric alcohols are heated at 50 to 150°C in the presence of a suitable catalyst such as para-toluenesulfonic acid without a solvent or using an inert solvent.
The ester is formed by reacting at a temperature of 2 to 10 hours. The compound (c) used in the present invention is an α-olefin/maleic anhydride copolymer or the α-
It can be obtained by hydrolyzing or partially hydrolyzing an olefin/maleic anhydride/dialkyl maleate terpolymer by a conventional method, or by further adding a light metal hydroxide to form a light metal salt.
For example, to hydrolyze an α-olefin/maleic anhydride copolymer, an equivalent or slightly excess amount of water is added, and the mixture is heated and stirred at a temperature of 100°C or lower, preferably 50 to 80°C. In addition, for partial hydrolysis, the same operation may be performed by adding less than the equivalent amount of water. Light metal salts are prepared by adding an amount of light metal hydroxide corresponding to the desired salt to a hydrolyzate or partial hydrolyzate of α-olefin/maleic anhydride copolymer, and heating the mixture at a temperature of 80 to 150°C. , by removing the produced water from the reaction system. Light metals that can be used in the present invention include lithium, sodium, potassium, calcium, magnesium, aluminum, and the like. In addition, compound (d) can be obtained by reacting an α-olefin/maleic anhydride copolymer with a monohydric alcohol having 1 to 5 carbon atoms in an amount less than the equivalent amount to perform partial alkyl esterification, and if necessary, further perform the above-mentioned method. Add a light metal hydroxide to make a light metal salt, or
The obtained partially alkyl esterified product was added to the above compound.
As in the case of (c), it can be obtained by hydrolysis, partial hydrolysis, and further formation of a light metal salt. The esterification reaction is usually carried out without a solvent or using an inert solvent at a temperature of 50 to 150°C. Monohydric alcohols that can be used include those mentioned above. The fuel oil additive of the present invention can be used in the form of a concentrated solution of 10 to 80% by weight, preferably 30 to 60% by weight, in an aromatic solvent such as toluene, xylene, or kyumene, or in a mineral oil such as kerosene or diesel oil. can. The fuel oil additive of the present invention may optionally contain compounds conventionally known as flow improvers for fuel oil, such as ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer.
Acrylate copolymers, halogenated polyalkylenes, alkyl (meth)acrylate polymers, condensates of chlorinated paraffins and naphthalene, nitrogen-containing derivatives of alkenylsuccinic acids, aliphatic dicarboxylic acid amides, and the like can also be blended. These conventional fluidity modifiers can be blended in the fluidity modifier of the present invention, usually about 0 to 98% by weight, preferably 0 to 50% by weight. Furthermore, it can also be used in combination with other common fuel oil additives, such as antioxidants and corrosion inhibitors. [Function] It is not necessarily clear why the fuel sulfur oil additive of the present invention can impart good low-temperature fluidity to heavy gas oil, gas oil made by mixing vacuum gas oil and cracked gas oil, A heavy oil, etc. This is thought to be due to the following characteristics. The fuel oil additive of the present invention is composed of a compound having a linear carbon chain length approximately equal to the carbon chain length of the precipitated wax, and furthermore, the fuel oil additive of the present invention precipitates almost simultaneously with the wax ( (almost the same solubility in fuel oil). Therefore, it is thought that this is because when fuel oil is exposed to low temperatures, it easily forms a eutectic with wax, and the wax/additive eutectic is dispersed in the fuel oil in a small state, preventing wax crystals from growing any further. . [Examples] The present invention will be specifically described below with reference to Examples and Production Examples, but the present invention is not limited to these Examples. Production example 1 α-olefin with 20 to 28 carbon atoms (Mitsubishi Chemical Industries, Ltd.
Co., Ltd., Diaren 208, C ₁₈ : 0.5%, C ₂₀ : 28%,
_C22 : 25%, _C24 : 19%, _C26 : 15%, _C28 : 9%,
Charge 223.3 g (0.7 mol) of C ₃₀ or higher: 3.5%), 68.6 g (0.7 mol) of maleic anhydride, and 291.9 g of xylene into a four-necked flask equipped with a reflux condenser, and heat at 80°C in a nitrogen stream. Heat and stir. Next, 2.3 g (0.014 mol) of azobisisobutyronitrile (hereinafter abbreviated as AIBN) was added as a radical initiator, and the mixture was reacted at 80° C. for 5 hours. Further AIBN 1.15
g (0.007 mol) was added and reacted for 3 hours. The saponification value of the copolymer produced after xylene removal is 264,
The number average degree of polymerization determined by gel permeation chromatography (hereinafter abbreviated as GPC) was 15.6. Production Example 2 166.8 g of a 50% by weight xylene solution of the copolymer obtained in Production Example 1 and 10 g of distilled water were placed in a 300 ml four-necked flask equipped with a water separator equipped with a reflux condenser, and heated at 80°C for 50 minutes. The mixture was stirred for hours to obtain a hydrolyzate (α-olefin/maleic acid copolymer). Excess distilled water was removed azeotropically. After removal of xylene, this hydrolyzate had an acid value of 263 and a number average degree of polymerization of 15.6. Production Example 3 184.4 g of the 50% by weight xylene solution of the α-olefin/maleic acid copolymer obtained in Production Example 2 and 16 g of sodium hydroxide were placed in a 300 ml four-necked flask equipped with a water separator equipped with a reflux condenser. ,140~150℃
The mixture was heated and stirred for 1 hour while separating the produced water to obtain the sodium salt of the copolymer. Production example 4 α-olefin with a carbon number of 30 to 60 (manufactured by Mitsubishi Chemical Industries, Dialene 30, C ₂₈ or less: 5%, C ₃₀ or more: 95
%) 289g (0.5 mol) and dimethyl maleate 72
(0.5 mol) and 361 g of xylene were placed in a four-necked flask equipped with a reflux condenser, and the mixture was heated in a nitrogen stream.
Heat and stir to 80℃. Then as a radical initiator
1.64 g (0.01 mol) of AIBN was added and reacted at 80°C for 5 hours. Additionally, 0.82g (0.005mol) of AIBN
was added and reacted for 3 hours. The saponification value of the resulting polymer after xylene removal was 155, and the number average degree of polymerization by GPC was 14.1. Production example 5 α-olefin with 30 to 60 carbon atoms (manufactured by Mitsubishi Kasei,
Dialen 30, C ₂₈ or less: 5%, C ₃₀ or more: 98%)
289 g (0.5 mol), maleic anhydride 24.5 g (0.25 mol), dimethyl maleate 36 g (0.25 mol), and xylene 349.5 g were placed in a four-necked flask equipped with a reflux condenser and heated to 80°C in a nitrogen stream. Stir. Next, 1.64g of AIBN as a radical initiator
(0.01 mol) was added and reacted at 80°C for 5 hours.
Furthermore, 0.82 g (0.005 mol) of AIBN was added and reacted for 3 hours. After xylene was removed, the resulting polymer had a saponification value of 161 and a number average degree of polymerization of 7.3. Production Example 6 166.8g of the 50% by weight xylene solution of the copolymer obtained in Production Example 1 and 1.8g of distilled water were placed in a 300ml four-necked flask equipped with a reflux condenser, stirred at 80°C for 5 hours, and partially hydrated. A decomposition product was obtained. The number average degree of polymerization of this partial hydrolyzate after removal of xylene was 15.6, and the hydrolysis rate was approximately 40% based on the infrared absorption spectrum. Production Example 7 166.8 g of a 50% by weight xylene solution of the copolymer obtained in Production Example 1 and 14.8 g of n-butanol were charged into a 300 ml four-necked flask equipped with a reflux condenser.
The mixture was stirred at 100°C for 5 hours to obtain a partially esterified product.
The acid value of this partially esterified product after xylene removal is
114, and the number average degree of polymerization was 15.6. Production Example 8 In the same manner as in Production Example 1, α-olefin having 16 to 18 carbon atoms (manufactured by Mitsubishi Chemical Industries, Ltd., Dialene 168,
A copolymer of C ₁₈ : 57%, C ₁₈ : 43%) and maleic anhydride was obtained. The saponification value of the copolymer produced is 332,
The number average degree of polymerization by GPC was 14.6. Example 1 The low-temperature fluidity of light oil A, light oil B, or heavy oil A in Table 1 in which the improver containing the copolymer produced in Production Examples 1 to 5 was blended was tested. Light oil A is a straight-run light oil obtained by deep drawing of atmospheric distillation. Furthermore, light oil B and A heavy oil are mixtures of heavy light oil and cracked light oil, as shown in Table 1.
The heavy oil also contains a small amount of residual oil. The test is based on JIS K2269-1980 pour point (pp) and British standard.
This was done by measuring the cold overloading point (CFPP) of IP-309. The results are shown in Table 2.

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〔Effect of the invention〕

As specifically shown in the examples, the fuel oil fluidity improver of the present invention can be added to fuel to improve straight run gas oil, A
Good low-temperature fluidity can be imparted not only to heavy oil but also to heavy gas oil, gas oil that is a mixture of vacuum gas oil and cracked gas oil, and A heavy oil. Although the fluidity improver of the present invention varies depending on the composition, properties, etc. of the fuel oil, it can usually achieve its purpose by blending it in the fuel oil at a concentration of 10 to 10,000 ppm.

Claims (1)

[Scope of Claims] 1 The following (a) to (d) (a) α-olefin having 20 to 60 carbon atoms, maleic anhydride and dialkyl maleate (provided that the alkyl group has 1 to 5 carbon atoms) ) with a number average degree of polymerization of 2 to 50; (b) α-olefin with 20 to 60 carbon atoms and dialkyl maleate (however, the number of carbon atoms in the alkyl group is 1 to 50);
5) with a number average degree of polymerization of 2 to 50; (c) the compound of (a) above or α- having 20 to 60 carbon atoms;
A hydrolyzate or partial hydrolyzate of a copolymer of olefin and maleic anhydride with a number average degree of polymerization of 2 to 50, or a light metal salt thereof; (d) α-olefin having 20 to 60 carbon atoms and anhydride; A copolymer with maleic acid with a number average degree of polymerization of 2 to 2.
50 partially alkyl esterified products (however,
At least one compound selected from the group consisting of: A fuel oil additive.