阅读说明：本技术 一种柴油 (Diesel oil ) 是由 杨啟华 于 2019-09-19 设计创作，主要内容包括：本发明主要使用了石化柴油、一元醇、纳米氧化物和其他助剂,得到了具有优异性能的柴油。实验测试结果表明,本发明制备得到的柴油经炭烟颗粒排放量测试和氮氧化合物的排放量测试显示,所排放的尾气中烟雾和氮氧化合物的量远低于国家的排放限值,尾气排放烟雾量和氮氧化合物量显著降低；经十六烷值测试显示,所得柴油的十六烷值高于GB 19147-2016《车用柴油》对十六烷值的质量指标。此外本发明制备的柴油用于发动机后,发动机动力显著提升10％、消耗降低10％,且发动机制动热效率较高,所得柴油具有抗静电作用,并对于发动机内部零件起到保护作用,且制备工艺流程简单,具有很强的工业应用价值和发展前景。(the invention mainly uses the petroleum diesel, monohydric alcohol, nano oxide and other auxiliary agents to obtain the diesel with excellent performance. Experimental test results show that the diesel prepared by the invention is subjected to soot particle emission tests and nitrogen oxide emission tests, and the amount of smoke and nitrogen oxide in the emitted tail gas is far lower than the national emission limit value, so that the amount of smoke and nitrogen oxide emitted by the tail gas is remarkably reduced; the cetane number of the obtained diesel oil is higher than the quality index of GB19147-2016 (diesel oil for vehicles) on the cetane number through a cetane number test. In addition, after the diesel prepared by the invention is used for an engine, the power of the engine is obviously improved by 10%, the consumption is reduced by 10%, the braking thermal efficiency of the engine is higher, the obtained diesel has an antistatic effect and plays a role in protecting internal parts of the engine, the preparation process flow is simple, and the diesel has a strong industrial application value and a strong development prospect.)

1. The diesel oil is characterized by comprising the following raw materials in parts by mass: 60-70 parts of petroleum diesel, 15-25 parts of monohydric alcohol, 5-7 parts of smoke suppressor, 6-10 parts of nano oxide, 6-8 parts of pH balancing agent and 6-10 parts of antistatic agent.

2. A diesel fuel according to claim 1, wherein the petroleum diesel fuel is selected from the group consisting of 0# diesel fuel, 10# diesel fuel, and-10 # diesel fuel.

3. A diesel fuel according to claim 1 or 2 wherein the monohydric alcohol is selected from one or more of methanol, ethanol and butanol.

4. The diesel fuel of claim 1, wherein the smoke suppressor is selected from one or more of tung oil, coconut oil and rapeseed oil.

5. A diesel fuel as claimed in claim 4, wherein the smoke suppressant is tung oil and coconut oil.

6. The diesel oil of claim 1, wherein the nano-oxide is selected from one or more of nano-titanium dioxide, nano-zirconium dioxide and nano-tin dioxide.

7. A diesel fuel as claimed in claim 6, characterized in that said nano-oxide is nano-titania.

8. A diesel fuel as claimed in claim 1, characterized in that the pH balancing agent is selected from one or more of diethanolamine, triethanolamine and tri-n-butylamine.

9. a diesel fuel according to claim 1, characterized in that the antistatic agent is polyethylene glycol and/or polypropylene glycol.

10. a process for the preparation of a diesel fuel according to any of claims 1 to 9, characterized by the following steps:

The method comprises the following steps: sequentially adding a smoke suppressor, a nano oxide and monohydric alcohol into a high-pressure reaction kettle, uniformly mixing at a stirring speed of 180-220 rpm at a reaction temperature of 80-120 ℃ and a reaction pressure of 3-5 MPa, and cooling to room temperature to obtain a mixture A;

Step two: and (3) uniformly mixing and stirring the petroleum diesel, the pH balancing agent, the antistatic agent and the mixture A obtained in the step one for 1-2 hours at normal temperature and normal pressure to obtain the catalyst.

Technical Field

The invention relates to the field of energy fuels, in particular to diesel oil.

Background

with the continuous development of the industry in China, the demand of petrochemical resources is increasing day by day, and diesel engines are widely applied to various fields of national economy due to the characteristics of high thermal efficiency, high output torque and the like. Petroleum diesel is a common traditional diesel engine fuel, but with the continuous updating and upgrading of diesel engines, the current diesel engines have strict requirements on various performances such as power performance, wear resistance, low consumption performance and the like of diesel. The traditional petroleum diesel oil can not meet the use requirements of the diesel oil for vehicles, and can be put into use after being further refined.

In order to improve the lubricity, cetane number, conductivity, antistatic property, etc. of diesel oil, various additives, such as an antiwear agent, a cetane number improver, an antistatic agent, etc., are often added to diesel oil in the prior art. However, when a plurality of additives are mixed together, there is a problem that different additives affect each other. And because the diesel oil is often incompletely combusted due to poor atomization in an engine, carbon smoke Particles (PM) and Nitrogen Oxides (NO) are discharged_x) And a large amount of black smoke is formed. Most of nitrogen oxides discharged by the diesel engine are nitric oxide and a small amount of nitrogen dioxide, the nitric oxide is slowly oxidized in the air, but the nitric oxide is quickly converted into polluting gas nitrogen dioxide under the irradiation of ultraviolet rays; the carbon smoke particles discharged by the diesel engine can penetrate into the lung of a human body to damage the self-cleaning function of various channels in the lung, and meanwhile, a plurality of organic substances are adsorbed on the particles to have the mutagenic and carcinogenic effects to different degrees. Therefore, the improvement of the existing diesel oil is urgently needed, and a novel high-performance diesel oil is developed.

Disclosure of Invention

In order to solve the technical problem, the first aspect of the invention provides a diesel oil, which comprises the following raw materials in parts by mass: 60-70 parts of petroleum diesel, 15-25 parts of monohydric alcohol, 5-7 parts of smoke suppressor, 6-10 parts of nano oxide, 6-8 parts of pH balancing agent and 6-10 parts of antistatic agent.

As a preferred technical scheme, the petrochemical diesel oil is selected from one or more of 0# diesel oil, 10# diesel oil and-10 # diesel oil.

As a preferable technical scheme, the monohydric alcohol is selected from one or more of methanol, ethanol and butanol.

As a preferable technical scheme, the smoke suppressor is selected from one or more of tung oil, coconut oil and rapeseed oil.

As a preferred technical scheme, the smoke suppressor is tung oil and coconut oil.

As a preferable technical scheme, the nano oxide is selected from one or a combination of more of nano titanium dioxide, nano zirconium dioxide and nano tin dioxide.

As a preferable technical scheme, the nano oxide is nano titanium dioxide.

as a preferred technical scheme, the pH balancing agent is selected from one or more of diethanolamine, triethanolamine and tri-n-butylamine.

as a preferred technical solution, the antistatic agent is polyethylene glycol and/or polypropylene glycol.

the second aspect of the invention provides a preparation method of the diesel oil, which comprises the following steps:

The method comprises the following steps: sequentially adding a smoke suppressor, a nano oxide and monohydric alcohol into a high-pressure reaction kettle, uniformly mixing at a stirring speed of 180-220 rpm at a reaction temperature of 80-120 ℃ and a reaction pressure of 3-5 MPa, and cooling to room temperature to obtain a mixture A;

Step two: and (3) uniformly mixing and stirring the petroleum diesel, the pH balancing agent, the antistatic agent and the mixture A obtained in the step one for 1-2 hours at normal temperature and normal pressure to obtain the catalyst.

has the advantages that: the invention mainly uses the petroleum diesel, monohydric alcohol, nano oxide and other auxiliary agents to obtain the diesel with excellent performance. After the diesel prepared by the invention is used for an engine, the power of the engine is obviously improved by 10 percent, and the consumption is reduced by 10 percent. Experimental test results show that the diesel prepared by the invention is subjected to soot particle emission tests and nitrogen oxide emission tests, and the amount of smoke and nitrogen oxide in the emitted tail gas is far lower than the national emission limit value, so that the amount of smoke and nitrogen oxide emitted by the tail gas is remarkably reduced; the cetane number of the obtained diesel oil is higher than the quality index of GB19147-2016 (diesel oil for vehicles) on the cetane number through a cetane number test. In addition, the engine braking thermal efficiency is higher, the obtained diesel oil has an antistatic effect and a protection effect on internal parts of the engine, and the preparation process flow is simple, so that the diesel oil has a very strong industrial application value and a very strong development prospect.

Detailed Description

The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.

The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

in order to solve the technical problem, the first aspect of the invention provides a diesel oil, which comprises the following raw materials in parts by mass: 60-70 parts of petroleum diesel, 15-25 parts of monohydric alcohol, 5-7 parts of smoke suppressor, 6-10 parts of nano oxide, 6-8 parts of pH balancing agent and 6-10 parts of antistatic agent.

In a preferred embodiment, the diesel oil comprises the following raw materials in parts by mass: 65 parts of petroleum diesel, 20 parts of monohydric alcohol, 6 parts of smoke suppressor, 8 parts of nano oxide, 7 parts of pH balancing agent and 8 parts of antistatic agent.

< petrochemical Diesel oil >

the petroleum diesel is a light petroleum product, is a complex hydrocarbon (with the carbon number of about 10-22) mixture, and is widely applied to large vehicles, railway locomotives and ships. The petroleum diesel oil is divided into light diesel oil (the boiling point range is about 180-370 ℃) and heavy diesel oil (the boiling point range is about 350-410 ℃). Wherein, the light diesel oil has six grades of 5, 0, -10, -20, -35 and-50 and the heavy diesel oil has three grades of 10, 20 and 30 according to the grade of the condensation point.

In a preferred embodiment, the petrochemical diesel oil is selected from one or more of 0# diesel oil, 10# diesel oil and-10 # diesel oil.

In a more preferred embodiment, the petrochemical diesel is # 0 diesel.

The 0# diesel oil is purchased from Shanghai Pusheng petrochemical company Limited and has the model of 0# diesel oil.

Petroleum diesel is a common traditional diesel engine fuel, but with the continuous updating of diesel engines, the current diesel engines have strict requirements on various performances such as power performance, wear resistance and the like of diesel. The traditional petroleum diesel oil can not meet the use requirements of the diesel oil for vehicles, and can be put into use after being further refined. And because the diesel oil is often incompletely combusted due to poor atomization in an engine, carbon smoke Particles (PM) and Nitrogen Oxides (NO) are discharged_x) And a large amount of black smoke is formed. Most of nitrogen oxides discharged by the diesel engine are nitric oxide and a small amount of nitrogen dioxide, the nitric oxide is slowly oxidized in the air, but the nitric oxide is quickly converted into polluting gas nitrogen dioxide under the irradiation of ultraviolet rays; the carbon smoke particles discharged by the diesel engine can penetrate into the lung of a human body to damage the self-cleaning function of various channels in the lung, and meanwhile, a plurality of organic substances are adsorbed on the particles and have the mutagenic and carcinogenic effects of different degrees.

< monohydric alcohol >

Monohydric alcohol means a compound containing only one hydroxyl group in the molecule.

In a preferred embodiment, the monohydric alcohol is selected from one or more of methanol, ethanol, butanol.

In a preferred embodiment, the monohydric alcohol is methanol.

The inventor finds that when monohydric alcohol, especially methanol, is added into the petroleum diesel fuel, the power performance of the diesel fuel can be improved to a certain extent, the fuel consumption is reduced, and the exhaust gas smoke emission is reduced. The inventor believes that adding a certain amount of methanol into petroleum diesel can increase the oxygen content in the fuel, reduce the particulate matter emission of the diesel engine, and improve the torque and power of the engine, thereby improving the braking thermal efficiency and braking torque of the engine, and reducing the braking oil consumption. But methanol and diesel oil have certain difference due to inherent properties and have poor compatibility; and the addition of methanol increases the corrosiveness of metal materials and the swelling property of rubber materials in the engine, influences the service life of the engine, so that further improvement is needed in the practical use.

< smoke suppressor >

The smoke suppressor is an additive added into fuel to improve the dynamic performance of motor vehicles and reduce the smoke discharge.

In a preferred embodiment, the smoke suppressant is selected from one or more of tung oil, coconut oil and rapeseed oil.

In a more preferred embodiment, the smoke suppressant is a mixture of tung oil and coconut oil.

In a further preferred embodiment, the mass ratio of the tung oil to the coconut oil in the smoke suppressor is (1.5-2.5): 1.

In a further preferred embodiment, the mass ratio of tung oil to coconut oil in the smoke suppressant is 2: 1.

Tung oil, known by the English name Tung oil, is excellent dry vegetable oil, has the characteristics of quick drying, light specific gravity, good glossiness, strong adhesive force, heat resistance, acid resistance, alkali resistance, corrosion resistance, rust resistance, non-conductivity and the like, and has wide application.

Coconut oil, English name Coconut oil, CAS number 8001-31-8, is the alias Coconut oil. Coconut oil is obtained from coconut meat (dried) and is a white or yellowish fat.

The tung oil is purchased from Tongfa scientific and technology limited company in Zhang Jiajie.

The coconut oil is purchased from Wuhan Hua Xiang & Jie Biotech limited.

The inventors, when studying how to solve the problem of compatibility between the petroleum diesel and the monohydric alcohol, found that when a mixture of tung oil and coconut oil is added to the petroleum diesel, especially the mass ratio of tung oil to coconut oil is 2: 1, the compatibility problem of the petroleum diesel and the monohydric alcohol is improved, and the amount of exhaust smoke and fog of tail gas after the diesel is used can be reduced to a certain extent. The inventors believe that, on the one hand, the mixture of tung oil and coconut oil reduces the surface tension of the two-phase interface of the petroleum diesel and the monohydric alcohol, improving the compatibility of the petroleum diesel and the monohydric alcohol; on the other hand, the tung oil and the coconut oil contain longer fatty acid chains, higher saturation and higher oxygen content, thereby increasing the cetane number of the diesel oil, reducing the cracking tendency of the carbon smoke and further reducing the exhaust smoke quantity of the tail gas of the diesel engine. However, the fuel added with the tung oil and the coconut oil has higher acidity, which has certain influence on the function of other additives; meanwhile, the viscosity of the system is increased, and carbon deposition is easily formed; and the tung oil and the coconut oil increase the oxygen content of the obtained diesel oil, cause the formation amount of nitrogen oxide to be increased, and result in the increase of the nitrogen oxide emission of the engine.

< Nano oxide >

The nano oxide refers to an oxide with a particle size reaching a nanometer level.

in a preferred embodiment, the nano-oxide is selected from one or more of nano-titanium dioxide, nano-zirconium dioxide and nano-tin dioxide.

In a more preferred embodiment, the nano-oxide is nano-titania.

(Nano titanium dioxide)

The nano titanium dioxide is white loose powder, commonly called nano titanium dioxide, and has good dispersibility and weather resistance.

In a further preferred embodiment, the nano titanium dioxide is a modified nano titanium dioxide.

In a still further preferred embodiment, the modified nano titanium dioxide is phenyl triethoxysilane modified nano titanium dioxide.

In a preferred embodiment, the preparation method of the modified nano titanium dioxide comprises the following steps:

(1) adding 6-10 parts of nano titanium dioxide into 60-80 mL of solvent, carrying out ultrasonic treatment for 10-20 min, and uniformly mixing to obtain a mixed solution A;

(2) Adding 4-6 parts of phenyl triethoxy silane and 1-3 parts of glacial acetic acid into the mixed solution A prepared in the step (1) under the stirring condition, and stirring and reacting for 1.5-2.5 h at 70-90 ℃ to obtain a uniform mixed solution B;

(3) and (3) carrying out centrifugal separation, washing, drying and grinding on the mixed solution B prepared in the step (2) to obtain the modified nano titanium dioxide.

In a more preferred embodiment, the modified nano titanium dioxide is prepared by the following method:

(1) adding 8 parts of nano titanium dioxide into 70mL of solvent, and carrying out ultrasonic treatment for 15min to uniformly mix the solution to prepare a mixed solution A;

(2) Adding 5 parts of phenyl triethoxy silane and 2 parts of glacial acetic acid into the mixed solution A prepared in the step (1) under the stirring condition, and stirring and reacting for 2 hours at 80 ℃ to obtain a uniform mixed solution B;

(3) And (3) carrying out centrifugal separation, washing, drying and grinding on the mixed solution B prepared in the step (2) to obtain the modified nano titanium dioxide.

In a more preferred embodiment, the nano titanium dioxide has a particle size of 25 to 35 nm.

in a further preferred embodiment, the nano-titania has a particle size of 30 nm.

The phenyltriethoxysilane was purchased from Wuhana white pharmaceutical chemical Co., Ltd, CAS number: 780-69-8, purchased from Viruna chemical Co., Ltd, Guangzhou.

the nano titanium dioxide with the particle size of 30nm is purchased from Shanghai ink high-tech materials, Inc. and has the model of MG-Ti 012.

The inventor finds that when the nano titanium dioxide is added into the system in the research process, the power of an engine can be effectively improved, the exhaust smoke fog can be reduced, the emission of nitrogen oxides can be reduced, the viscosity of the system can be reduced, and the carbon deposition probability can be reduced. The inventor conjectures that the reason for this is that the addition of the nano titanium dioxide can promote the formation of short chain molecules in the system and reduce the viscosity of the system; meanwhile, the system is initiated to be completely combusted, the emission of nitrogen oxides is reduced, the formation of soot particles and the adsorption and aggregation of other components such as sulfate, metal oxide and the like are reduced, and the formation of soot Particles (PM) is finally reduced.

However, the nano titanium dioxide has a very high specific surface area, is easily influenced by strong van der waals force to generate an agglomeration effect, and is not easily and uniformly dispersed in an oil product. In the actual use process, the inventor finds that the nanometer titanium dioxide modified by the phenyltriethoxysilane can obviously improve the dispersing ability of the nanometer titanium dioxide in a system. The inventor believes that one end of the phenyltriethoxysilane can form covalent bond with the surface of the nano titanium dioxide, the large steric hindrance structure of the other end is dissociated in the oil product, and the nano titanium dioxide particles are dragged to be uniformly dispersed in the oil product.

Meanwhile, the inventor surprisingly found that when the particle size of the nano titanium dioxide is 30nm and the mass part of the nano titanium dioxide is 8 parts, the exhaust smoke of the engine is remarkably reduced. The inventor conjectures that the addition of the nano titanium dioxide can obviously reduce the exhaust smoke amount, but the exhaust gas still contains a small part of soot particles; when the particle size of the nano titanium dioxide is 30nm and the mass part is 8 parts, a small amount of nano titanium dioxide and carbon smoke particles are adsorbed and agglomerated together and are taken out of the system; after the nano titanium dioxide is illuminated, a cavity effect is generated, organic matters adsorbed on the soot particles can be oxidized and decomposed into inorganic matter micromolecules such as water or carbon dioxide, and the generation of the soot particles is reduced. When the mass part of the nano titanium dioxide is too large, a large number of nano titanium dioxide particles are easily taken out of the system by the soot particles and discharged in tail gas, so that secondary pollution is caused; when the mass part of the nano titanium dioxide is too small, the corresponding effect can not be fully exerted; when the particle size of the nano titanium dioxide is too large, the abrasion to metal materials and rubber materials of an engine is serious, and the service life of the engine is shortened, so that the particle size and the mass part of the nano titanium dioxide are strictly controlled in the use process. However, because the nano titanium dioxide is used for improving the performance of diesel oil, the nano titanium dioxide is required to prevent abrasion of components in an engine in use, and the problem needs to be solved in the development process of the inventor.

< pH Balancing agent >

In a preferred embodiment, the pH balancing agent is selected from one or more combinations of diethanolamine, triethanolamine, tri-n-butylamine.

In a more preferred embodiment, the pH balancing agent is a mixture of diethanolamine and triethanolamine.

In a further preferred embodiment, the mass ratio of diethanolamine to triethanolamine in the pH balancing agent is 3: (3.5-4.5).

In a further preferred embodiment, the mass ratio of diethanolamine to triethanolamine in the pH balancing agent is 3: 4.

Diethanolamine, purchased from Hubei Xin Rundji, CAS number: 111-42-2.

The triethanolamine is purchased from Wuhan La Na white pharmaceutical chemical Co., Ltd, CAS number: 102-71-6.

When the mixture of diethanolamine and triethanolamine is added into the system, the pH value of the system can be effectively improved. This is because the unique polar groups on the molecules of diethanolamine and triethanolamine make it possible to adjust the pH of the system. And the inventor unexpectedly finds that when the mass ratio of the diethanol amine to the triethanol amine is 3: 4, besides the improvement of the pH value of the system, the corrosiveness of the monohydric alcohol to the metal material is also reduced. The inventors have considered that when the mass ratio of diethanolamine to triethanolamine is too small, the pH balancer may exhibit a certain anticorrosive effect on ferrous metals to some extent, but its pH adjusting performance may be lowered when used in an engine operating at high temperatures for a long period of time; when the mass ratio of the diethanol amine to the triethanol amine is too large, the pH balancing agent has certain high temperature resistance, but the anti-corrosion capability on metal is reduced to some extent; when the mass ratio of the ethanolamine to the triethanolamine is 3: 4, the two can cooperate sufficiently to reduce the corrosiveness of the monohydric alcohol to the metal material.

< antistatic agent >

antistatic agents are additives that are added to plastics or applied to the surface of molded articles to reduce the buildup of static electricity.

In a preferred embodiment, the antistatic agent is polyethylene glycol and/or polypropylene glycol.

In a more preferred embodiment, the antistatic agent is polyethylene glycol.

(polyethylene glycol)

Polyethylene glycol, PEG (Polyethylene glycol) for short, is formed by the gradual addition polymerization of ethylene oxide and water or ethylene glycol. Polyethylene glycol is a common antistatic agent, has good intermiscibility with a plurality of organic matter components, and has wide application in industries such as cosmetics, pharmacy, chemical fiber, rubber, plastics, paper making, paint, electroplating, pesticides, metal processing, food processing and the like.

In a more preferred embodiment, the polyethylene glycol is a polyethylene glycol having a relative molecular weight of 500 to 700.

In a further preferred embodiment, the polyethylene glycol is a polyethylene glycol having a relative molecular weight of 600 (CAS number: 25322-68-3).

The polyethylene glycol is purchased from Wuhan La Na white pharmaceutical chemical Co Ltd, and has the model of PEG-600.

As the diesel oil used in the invention inevitably generates static electricity during production, storage and transportation, the antistatic agent must be added during actual use. The inventor finds that when polyethylene glycol with the relative molecular weight of 500-700 is added, the antistatic effect of an oil product is achieved, the dispersing capacity of titanium dioxide is further improved, and abrasion of nanometer titanium dioxide to components in an engine is reduced. The inventor conjectures that the polyethylene glycol with the relative molecular weight of 500-700 covers and wraps the nano titanium dioxide particles through adsorption to form a steric hindrance effect, so that the nano titanium dioxide can be uniformly dispersed in a system; and polar groups in polyethylene glycol with the relative molecular weight of 500-700 can be adsorbed to the metal surface of an engine to form an oil film, so that mechanical abrasion is effectively reduced. And additives which can reduce the lubricating property of the antiwear agent, such as a cetane number improver, are not required to be added, so that the effects of reducing the smoke discharged by tail gas, remarkably improving the power by 10 percent, reducing the consumption by 10 percent and the like can be achieved.

The second aspect of the invention provides a preparation method of the diesel oil, which comprises the following steps:

The method comprises the following steps: sequentially adding a smoke suppressor, a nano oxide and monohydric alcohol into a high-pressure reaction kettle, uniformly mixing at a stirring speed of 180-220 rpm at a reaction temperature of 80-120 ℃ and a reaction pressure of 3-5 MPa, and cooling to room temperature to obtain a mixture A;

Step two: and (3) uniformly mixing and stirring the petroleum diesel, the pH balancing agent, the antistatic agent and the mixture A obtained in the step one for 1-2 hours at normal temperature and normal pressure to obtain the catalyst.

In a preferred embodiment, the preparation method of the diesel oil comprises the following steps:

The method comprises the following steps: sequentially adding the smoke suppressor, the nano oxide and the monohydric alcohol into a high-pressure reaction kettle, uniformly mixing at a stirring speed of 200rpm at a reaction temperature of 100 ℃ and a reaction pressure of 4MPa, and cooling to room temperature to obtain a mixture A;

Step two: and (3) uniformly mixing and stirring the petroleum diesel, the pH balancing agent, the antistatic agent and the mixture A obtained in the step one for 1.5 hours at normal temperature and normal pressure to obtain the catalyst.

The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.