JPH025451B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a surfactant. More specifically, the present invention heat-treats coal with an aromatic solvent, sulfonates the resulting liquefied oil, and then neutralizes it with an alkalizing agent to form a sulfonate, which is excellent as a dispersant and cement admixture. The present invention relates to a method for producing a surfactant having such effects.

Several techniques are already known for producing surfactants, such as cement admixtures, using coal as a raw material. For example, Japanese Patent Publication No. 33-4080 discloses an invention for producing a cement water reducing agent from humic-like substances contained in low-rank coal. Further, Japanese Patent Publication No. 47-39208 discloses an invention in which a cement water reducing agent is obtained by treating coal tar at a high temperature of 700 to 2000°C and then sulfonating it. However, when producing surfactants using these inventions, there are restrictions on the type of coal, or coal tar, which is a carbonized product of coal, must be treated at a high temperature of 700°C or higher. The surfactant obtained from such high-temperature treatment of coal tar is not always fully satisfactory for use as an admixture in cement or as a dispersant for slurry of water and solid fuel such as coal or petroleum coke. There are problems such as not exhibiting the surfactant effect that can be achieved.

The present invention provides a method for efficiently producing a surfactant using coal as a raw material, but using a method completely different from the known methods for producing surfactants as described above.

The present invention uses a compound having a 2- to 3-ring fused aromatic ring as a backbone, a compound obtained by hydrogenating at least one aromatic ring of these compounds, or a mixture thereof as a solvent, and coal in the solvent. After heat treatment in a temperature range of 200 to 500°C, preferably 300 to 450°C and under conditions not exceeding the critical temperature of the solvent, unreacted residues and solvent are removed, and the resulting liquefied oil is sulfonated. The present invention relates to a method for producing a surfactant, which is then neutralized using an alkalizing agent.

According to the present invention, coal of any coal type is used as a raw material, heat-treated under conditions of relatively low temperature and low pressure to obtain liquefied oil in a high yield, and this liquefied oil is converted into a sulfonate. This makes it possible to easily obtain a surfactant with excellent performance.

Next, the present invention will be explained in detail.

The liquefied coal oil that is the raw material for sulfonation of the present invention is prepared by heating any coal type and solvent at a temperature range of 200 to 500°C, preferably 300 to 450°C, and exceeding the critical temperature of the solvent. It is obtained by heat treatment under conditions that are not By using a compound having a 2- to 3-ring fused aromatic ring skeleton, a compound obtained by hydrogenating at least one aromatic ring of this compound, or a mixture thereof as a solvent, the process can be carried out at relatively low pressure and temperature. Liquefied oil can be obtained in good yield. Heat treatment as described above
It is carried out at a temperature of 200-500°C, preferably 300-450°C. If heat treatment is performed at a temperature higher than 500℃, the thermal decomposition of the coal will become more intense, increasing the production of low-boiling fractions, and the resulting liquefied oil will also be denatured by heat, so it will not be used as a dispersant or a sulfonate. It does not show effective action as a surfactant used in cement admixtures, etc. On the other hand, at temperatures lower than 200℃,
The yield of liquefied oil is too low for industrial use.

In the compound having a 2- to 3-ring condensed aromatic ring skeleton, the compound obtained by hydrogenating at least one aromatic ring of these compounds, or a mixture thereof used as a solvent in the present invention, 2- to 3-ring fused aromatic ring Typical specific examples of compounds having a fused aromatic ring as a skeleton include naphthalene, methylnaphthalene, anthracene, phenanthrene, acenaphthene, naphthol, etc. Hydrogenated products of these compounds can be prepared by methods known per se. Therefore, for example, using a cobalt-molybdenum oxide or sulfide as a catalyst, at a temperature of 300 to 450°C,
It can be easily obtained by hydrogenation treatment at a hydrogen partial pressure of 50 to 200 Kg/cm ² .

The pressure when heat-treating coal varies depending on the type of solvent used and, if hydrogen gas is used, its partial pressure, but generally it is 10 kg/
^cm2 or more.

In the present invention, when hydrogen gas is present in the heat treatment operation, it has the effect of increasing the liquefied oil yield, so the heat treatment operation may be performed in the presence of hydrogen gas.

The liquefied oil from which unreacted residues and solvent have been removed after the heat treatment operation is solid at room temperature. This solid coal liquefied oil is composed of many components with complex chemical structures, and although the details of each component are not clear, the main component is a component with a relatively small number of condensed rings. In contrast to coal tar. In other words, coal tar obtained by carbonizing coal is heat-treated at a high temperature of approximately 1000℃, which destroys the complex chemical structure that coal originally has, resulting in naphthalene, methylnaphthalene, anthracene, and benzpyrene. As a result, it contains a large amount of low-boiling point aromatic compounds such as. In this way, the main components of coal tar are components with a relatively small number of these condensed rings, so even if this is sulfonated and neutralized to form a surfactant, it cannot be used as a surfactant, for example, in cement. It does not show satisfactory effects as a surfactant for use as a cement admixture such as a water reducer, or as a dispersant for dispersing solid fuel fine powder such as petroleum coke or coal in water. I think so.

On the other hand, the liquefied coal oil used in the production of the surfactant of the present invention is obtained by heat treatment at a relatively low temperature. For this reason, the decomposition of the complex chemical structure of coal has not progressed very much, and when this is induced into surfactants, it is difficult to use surfactants, especially cement admixtures such as cement water reducers, or coal, petroleum coke, etc. It is thought that it exhibits a very effective action as a surfactant for uses such as a dispersant for dispersing solid fuel powder in water.

Next, the sulfonation method and the neutralization method using an alkalizing agent of the present invention will be described.

Methods for sulfonating aromatic compounds and condensed ring compounds are already known, and the sulfonation of liquefied coal oil in the present invention can also be carried out by methods similar to those known sulfonation methods.

As the sulfonating agent used for sulfonation, sulfonating agents such as sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or sulfuric anhydride are generally used, and these sulfonating agents can also be used in the present invention. is desirable. Among these sulfonating agents, sulfuric anhydride is particularly preferred from the viewpoint of improving the workability of the sulfonation reaction, improving the yield of the sulfonation reaction, and reducing the amount of by-product inorganic substances produced.

The amount of the sulfonating agent used is preferably 0.1 to 0.5 times the weight of the liquefied coal oil. If the amount used is less than 0.1 times the amount, the amount of sulfonic acid groups added to the liquefied petroleum oil will be small, which will not only make it difficult for the obtained surfactant to have sufficient performance, but also reduce the amount of sulfonated products produced. There is a problem with that. On the other hand, even if the amount used exceeds 5.0 times the amount, the amount of sulfonic acid groups added to coal liquefied oil does not increase, the yield of sulfonated products does not improve, and unreacted sulfonating agent is removed from the reaction product. This results in the disadvantage of having to do so.

There is no particular restriction on the reaction temperature for sulfonation, but
Generally, it is preferable to select from the range of 0 to 200°C. At a temperature lower than 0° C., there are disadvantages such as a decrease in the sulfonation reaction rate and coagulation of the sulfonation agent, making the reaction operation difficult. On the other hand, if the reaction temperature is higher than 200°C, problems such as the generation of heat due to the sulfonation reaction will become significant, making it difficult to control the reaction temperature.

In addition, since the liquefied coal oil of the present invention is obtained in a solid state at room temperature as described above, it is preferable to dissolve the liquefied coal oil in a suitable solvent and carry out the sulfonation reaction as a solution. The solvent is not particularly limited as long as it dissolves the liquefied coal oil and does not react with the sulfonating agent, but in practice, chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc. are used. is preferable.

The liquefied coal oil sulfonated by the method described above is then converted to a product useful as a surfactant by neutralization with an alkalizing agent.

In the production of surfactants, the technique of neutralizing a sulfonate with an alkalizing agent to form a sulfonate is already known, and neutralization methods using various alkalizing agents are known. In the present invention, it is preferable to employ these neutralization methods, and the alkalizing agent and reaction conditions may be selected according to known alkalizing agents and reaction conditions.

The surfactant obtained by the present invention is a sulfonate of liquefied coal oil (-SO ₃ M, where M is
Alkali metals such as Na and K, alkaline earth metals such as Mg, Ca, and Ba, or -NH ₄ , -
_NH2CH2CH2OH , _{-NH ( CH2CH2OH} ) _{2 ,} -N
(C ₂ H ₄ OH) ₃ and other organic amines). The surfactant obtained according to the present invention can be used as a dispersant for making an aqueous slurry from solid fuel such as fine coal or petroleum coke, or other water-insoluble fine powder, or as a cement water reducer. It is useful as an admixture for cement such as.

Next, Examples and Comparative Examples of the present invention will be shown.

Example 1 Production of liquefied coal oil Domestic A coal (moisture 1.6%,
Ash content 14.2%, volatile content 43.2%, fixed carbon 41.0%) 50
g and 2500 g of tetralin as a solvent with an internal volume of 0.5
The autoclave was placed in an autoclave equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas to remove the air inside, and the autoclave was sealed. While stirring the contents, the autoclave was heated to a temperature of 400°C using an electric furnace, and this temperature was maintained for 60 minutes. At this time, the pressure inside the autoclave was 25 Kg/cm ² . Next, after the autoclave was cooled to near room temperature, the contents were taken out, and the liquefied oil containing the solvent and the residue were separated by filtration. Then, the solvent was distilled off under reduced pressure to obtain a liquefied oil.
The liquefied oil yield was 55% by weight based on the charged coal (dry and ashless basis).

Sulfonation and Neutralization 7.0 g of coal liquefied oil obtained as described above.
was dissolved in 70 ml of methylene chloride and placed in a 300 ml three-necked flask (equipped with a stirring device, a device for cooling evaporated material, and a dropping funnel). While stirring the contents, sulfuric anhydride was slowly added dropwise from the dropping funnel. A total of 5.5 g of sulfuric anhydride was added dropwise over 30 minutes while maintaining the temperature of the contents at 25° C. during the dropwise addition. After completion of the dropwise addition, the mixture was aged at 45° C. for 60 minutes, and then methylene chloride was distilled off. Water was added to the sulfonation reaction product of liquefied coal oil remaining as a residue in the flask to form an aqueous solution, which was then taken out from the flask and neutralized to pH 7 by adding an aqueous solution of calcium hydroxide. The neutralized solution was filtered and water was distilled off under reduced pressure to obtain 6.8 g of calcium sulfonate as liquefied coal oil.

Performance Evaluation 3.25 g of calcium sulfonate of the liquefied coal oil obtained as described above was dissolved in water, and water was further added to make the total amount 293 g.

Container capacity of 650g of ordinary Portland cement: 4.7
After adding the calcium sulfonate aqueous solution of liquefied coal oil prepared above, the mixture was kneaded by hand, then at low speed, then at high speed, and then at low speed for 1 minute each.

Separately, place a flow cone (capacity) on a glass flat plate in advance.
83cm ³ , top diameter 25mm x bottom diameter 50mm x height 75mm)
A cement paste flow value measuring device was prepared, and the cement slurry immediately after mixing was put into this flow cone. Then, the flow cone was gently lifted and the diameter of the cement-water slurry spread on the glass plate was measured at two locations, and the average value of these values was taken as the flow value. Note that these kneading operations and measurement of flow values were carried out at a temperature of 20°C.

The flow value of the cement slurry was 182 mm.

Example 2 Production of liquefied coal oil 50g of tetralin and methylnaphthalene as solvent
Liquefied coal oil was obtained in the same manner as in Example 1, except that 200 g of the mixture was used and the autoclave was purged with nitrogen, then pressurized to 20 kg/cm ² with hydrogen gas and sealed. The liquefied oil yield was 63% by weight based on the charged coal (dry and ashless basis).

Sulfonation and Neutralization 7.0 g of coal liquefied oil obtained as described above.
Coal was prepared in the same manner as in Example 1, except that a solution of 70 ml of carbon tetrachloride was used, the amount of sulfuric anhydride used for sulfonation was changed to 9.8 g, and the reflux was performed under carbon tetrachloride reflux conditions. 12.6 g of calcium sulfonate in liquefied oil was obtained.

Performance Evaluation A cement flow test was conducted under the same conditions as in Example 1 using 3.25 g of calcium sulfonate from the liquefied coal oil obtained as described above. The flow value of the cement slurry was 188 mm.

Comparative Example 1 A commercially available lignin sulfonate water reducing agent was used in place of calcium sulfonate in liquefied coal oil, and a cement flow test was conducted under the same conditions as in Example 1. The flow value of the cement slurry was
It was 155mm.

Example 3 Production of liquefied coal oil Same as Example 1 except that 50 g of American B coal (moisture 3.8%, ash content 13.7%, volatile content 35.2%, fixed carbon 47.3%) was used instead of domestic A coal. The same operation as in 1 was carried out to obtain a liquefied oil with a yield of 35% by weight.

Sulfonation and Neutralization 12.0 g of coal liquefied oil obtained as described above.
was dissolved in 100 ml of methylene chloride, and 17.2 g of calcium sulfonate of coal liquefied oil was obtained by carrying out the same operation as in Example 1 except that 11.5 g of sulfuric anhydride was added dropwise over 60 minutes.

Performance evaluation Australian C coal (moisture 3.6%, ash 13.3%, volatile content 33.0
%, fixed carbon 50.1%) to a specific gravity liquid (specific gravity
1.35), and the floating coal was ground in a ball mill to prepare pulverized coal of 250 μm or less.

Water was added to the pulverized coal having a dry weight of 64% so that the total amount was 100 g. To this was added 0.5 g of calcium sulfonate from the liquefied coal oil obtained above and mixed for 5 minutes using a high speed homogenizer (manufactured by Tokushu Kakoki Co., Ltd.) to prepare a pulverized coal-water slurry. Immediately after mixing, the slurry was transferred to a container for viscosity measurement, and the viscosity was measured at 27°C using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).The viscosity of the slurry was 3200c.
It was p.

Comparative Example 2 A commercially available polycarboxylic acid type anionic surfactant was used instead of calcium sulfonate in the liquefied coal oil, and was added to and mixed with a pulverized coal-water slurry under the same conditions as in Example 3, but the viscosity of the slurry was 10000c.p.
As a result, there was no liquidity.

Claims (1)

[Claims] 1. A compound having a 2- to 3-ring fused aromatic ring as a skeleton, a compound obtained by hydrogenating at least one aromatic ring of these compounds, or a mixture thereof is used as a solvent, and coal is heated in the solvent.
After heat treatment at a temperature in the range of 200 to 500 °C and under conditions not exceeding the critical temperature of the solvent, unreacted residues and solvent are removed, the resulting liquefied oil is sulfonated, and then an alkalizing agent is used. A method for producing a surfactant, which comprises neutralizing the surfactant.