JPH0470587B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to the use of high boiling point oil which is inevitably produced in large quantities in the coal hydrocracking industry under high temperature and high pressure conditions. High-boiling point fractions have lower commercial value than low-boiling point fractions, which hinders improvements in industrial productivity and economic efficiency. There are few attempts to convert this high-boiling fraction into high value-added substances. The present invention is capable of producing an expensive packing material for high-performance liquid chromatography by high-pressure carbonization of a coal liquefied boiling point fraction, and that it is possible to use pure water as a mobile phase, which is a feature of this packing material, making it possible to conduct industrial separations. If applied to the target large-capacity chromatography equipment and used to separate physiologically active substances such as sugars and amino acids, it will contribute to the development of bio-related industries, which are currently in the process of development. Conventional technology In the pre-war direct coal liquefaction industry, 5 parts of hydrogen was added to 100 parts of pure coal, and the coal powder was produced by reaction in order to turn it into a fluid state when pumping the coal into a high-pressure reactor. All 130 parts of high boiling point heavy oil in the liquefied oil is used as blended oil.
(Reference: Chemical Engineering Vol. 40, No. 3 (1976), Minoru Morita) For this reason, the high boiling point heavy oil produced was used repeatedly, and the mixing ratio of coal to blended oil of 4:6 became established. It was. For this reason, there was no idea or attempt to use high boiling point heavy oil to produce substances with high added value. Research into the direct coal liquefaction industry (Japan's Sunshine Project) after the war included hydrogenation of the aforementioned heavy oil using a separate device to convert the heavy oil into a blended oil with strong hydrogen donating properties, and the subsequent hydrocracking reaction. We are moving in the direction of contributing to the This increases the production of light oil with high added value. (References Collection of papers from the symposium on coal liquefaction, 30th Hokkaido Coal Study Group, 1982, 2
(Monday 17th) Although there is a decrease in the amount of compounded oil used repeatedly due to the lighter weight of heavy oil, it is thought that this will be compensated for compared to other tar industries. Therefore, serious consideration has been given to producing products with high added value using surplus heavy oil as in the present invention. The technology for utilizing heavy oil produced by coal liquefaction is not advanced, and there are only a few trials to produce needle coke related to the production of electrodes for aluminum production, such as NCB in the UK, BF in West Germany,
It is reported that this was carried out at Mitsui Coke in Japan. (Reference: 1985 Sunshine Plan Subsidy Project Commissioned by New Energy Development Organization - Applications and Refining Technology of Coal Liquefaction Products - Fuel Association, March 1985) In addition to this, there are other foreseeable items as carbon material raw materials. Although several types have been mentioned, none have suggested the production of fillers for separation of organic substances as in the present invention. A column packing material for liquid chromatography is disclosed in Published Patent Publication No. 1983-41351, which relates to optically anisotropic small spheres of 1 to 10 μm obtained by heating pitches to 320 to 500°C. It is. The present invention uses a high boiling point fraction, not Pits, as a raw material with an H/C atomic ratio of 1.17 to 1.25, which is liquid at room temperature. This is a completely new and different method. Problems to be Solved by the Invention As mentioned earlier, the light boiling point fraction of directly liquefied coal oil is valuable as a clean fuel oil, but the high boiling point fraction is of low value. It is important to consider the secondary processing of high-boiling fractions of coal liquefied oil, which is relatively expensive to produce compared to petroleum. Compared to pitches that are solid at room temperature, high-boiling fractions that are liquid are advantageous in the production of carbon materials. In addition, the ash content and heavy metals are lower than that of pitcher, and the carbonized product is relatively fine, so it is thought that it can be used as an industrial material for producing fine chemicals. The industrial chromatogram packing materials currently in use are expensive. The reason for this is that the technology for producing products with consistent performance for each lot has not yet been established. It is also thought that this is due to subtle changes in the surface condition of the filler during processing. Therefore, it is necessary to research fillers that do not require surface treatment. Furthermore, even if the mobile phase is to be recovered and reused, if an organic solvent is used, the cost will be high and the consumption will be considerable. If pure water is used as the mobile phase here, the economical efficiency will be improved. Therefore, it is desired to produce a liquid chromatogram packing using pure water as a mobile phase. Means to solve the problem The properties of coal liquefied oil differ depending on the type of coal used as the raw material, but the reason for this difference is that the composition of the main aromatic group is almost constant, and the difference lies in the ratio of the amount of unit substances produced. Only. It is said that the structural compositions of aromatics are similar. However, there are large differences in the content of polar groups such as oxygen and nitrogen depending on the type of coal. It is said that the structure, composition, etc. of the high-boiling fraction in question here does not vary greatly depending on the type of coal. Based on the premise that Japan's coal direct liquefaction bench scale equipment currently in operation under the Sunshine Project is 2.4 tons/day,
Two representative high-boiling fractions of Illinois coal liquefied oil and Wandwan coal liquefied oil produced at a rate of 0.1 t/day are selected as raw materials to produce a liquid chromatogram packing material and the scope of application of the product. In particular, we investigated the case where pure water was used as the mobile phase. EXAMPLES Next, the present invention will be explained using examples, but the present invention is not limited thereto. Example 1 Continuous high temperature and high pressure hydrocracker (0.1t, 2.4t/
Put 15g of the high boiling point fraction of directly liquefied oil (Illinois coal or Wandwan coal) into an autoclave, replace the air with nitrogen gas, and reduce the initial pressure to 0Kg/cm ² , 10, 25, 50Kg/ cm ² and the primary carbonization conditions were 600°C for 2 hours. The temperature-pressure curve during this period was as shown in FIG. 1, and the reaction was carried out under high-pressure pyrolysis gas. The unreacted liquid material in the primary carbonization reaction was poured out of the autoclave, the solid material was thoroughly washed with benzol, the solid material was filtered with a glass filter, dried, and ground into 200 to 300 meshes and weighed. The yield of solids, which are carbonized products, is shown in Table 1. The yields varied depending on the initial gas pressure, but with Norinoi coal, the liquefied oil high boiling point fraction was about 30 to 51% Wandwan coal. In the liquefied high-boiling fraction, primary carbide was obtained with a high yield of 34.0%.

【table】

【table】

[Table] To secondary carbonize the primary carbide, put the crushed primary carbide into another small autoclave 4.2 to 4.5
g, replace the air with inert gas, and heat at 800°C or 700°C for 30 minutes at an initial pressure of 0 or 10 kg/cm ² to form a secondary carbide. The yield here was about 90-93% of primary carbonized solids. In addition, the carbide crushed into 200 to 300 meshes progressed to condensation or agglomeration in the secondary carbonization reaction and did not become a single mass, and the shape remained almost unchanged from that of the primary carbide. Table 2 shows Norinoi Charcoal Liquefied Heavy Oil Secondary Carbide 800
The elemental analysis values of the carbide produced after 30 minutes at ℃ are shown. This secondary carbide was packed into an analytical high-performance liquid chromatography column, and separation tests of various organic substance solutions and aqueous saccharide solutions, which are water-containing hydrocarbon substances, were conducted. Table 3 shows the model solute system for aromatics used in the test and the measurement conditions. The chromatogram is shown in FIG.

[Table] Figure 2 shows a chromatogram under the conditions of the experiment numbers in Table 3. The detection was performed using an ultraviolet spectrophotometer (UV). Experiment 1 in FIG. 2 shows the separation performance of the polycyclic aromatic solute benzene-naphthalene-biphenyl in terms of retention time. Experiment No. 2 is a separation chromatogram of nitrobenzene-metanitrobenzene-1.3.5nitrobenzene, which is a nitro derivative of benzene. Experiment No. 3 This is a chromatogram in which nitrobenzene isomers, orthonitrobenzene-metanitrobenzene, were separated. Experiment No. 4 is a chromatogram for the separation of the basic substance aniline-paraphenylenediamine. Experiment No. 5 is a chromatogram for the separation of basic substances pyridine and benzene. It has been found that the secondary carbide of the high-boiling fraction of directly liquefied oil from coal can separate the mixed solute system shown in Table 3 under these conditions from the aromatic group and its polar group-containing substances. Within the scope of the present invention, temperature selection for secondary carbonization conditions for high boiling point fractions in directly liquefied coal oil was determined through the following experiment. In other words, Illinois coal liquefied oil is part 1.
Next carbide in inert gas at 600℃, 700, 800, 900
The mobile phase of a mixed solute of bensol, naphthalene, and diphenyl was mixed with methanol 8:H ₂ O.
2, the separation performance was investigated. The results are shown in Figure 3. 1 in FIG. 3 is shown as a comparative object, and the three components are well separated by secondary carbide of n-paraffin based on patent application No. 63568/1989 submitted by the inventors. 2 is primary carbide (600℃)
As it is, the chromatogram has some slight differences, but it cannot be said that there is separation. 3 is 700℃
The separation performance of the chromatograph is becoming clear as three peaks appear from the secondary carbonization. 4
is carbonized at a secondary carbonization temperature of 800℃, and (3) is 700℃.
The separation performance is improved by this temperature, which is considered to be the optimum temperature. No. 5 was carbonized at 900°C, and only two peaks appeared, resulting in poor separation performance. Therefore, in addition to limiting the secondary carbonization temperature to 800°C, primary carbides of different types of coal are
As shown in the figure, there are cases where the secondary carbonization temperature is selected to be 700°C. FIG. 4 shows an experiment regarding the selection of the secondary carbonization temperature of the WandWan liquefied carbon. This is the same chromatogram as before for the separation of aromatic polycyclic substances, and 6 is the primary carbonization.
The product carbonized at 600°C has two clear peaks, as well as an additional small peak, and the separation is not sufficient. No. 7 was subjected to secondary carbonization at 700℃, and three peaks are clearly visible, which is considered to be an appropriate temperature. Sample No. 8 was carbonized at a secondary carbonization temperature of 800°C, and its separation performance was lower than that of (7). One of the features that can be applied to large-scale separation liquid chromatography within the scope of the present invention is that it uses pure water as a mobile phase and has separation performance for water-containing hydrocarbons "carbohydrates" as described below. . Secondary carbonization of Illinois charcoal liquefied oil Using 800℃ as column packing material, pure water as mobile phase, and solutes as glucose, fructose, sucrose, maltose, and lactose.
FIG. 5 shows the retention time (minutes) of each substance. It was difficult to separate glucose and fructose because their retention times were almost similar. Since the peaks of glucose and sucrose appear a little earlier in the case of glucose, we decided to investigate the separation performance of chromatography using a mixture of glucose and sucrose. Figure 6 shows the separation performance and quantitative properties of secondary carbides in the Illinois coal liquefaction high boiling point fraction of the present invention, where a is the secondary carbonization temperature.
700°C, b indicates the secondary carbonization temperature of 800°C. The mobile phases a and b are pure water and the flow rate is 1c.c./
The detector used was a differential refractometer (RI), and the chart speed was 30 cm/h. Retention times were determined using 10μ of solute samples containing 1% glucose and 1% sucrose in pure water. Furthermore, using 10μ of each solution for a total of 20μ, the separation and quantitative performance of AHB was determined by determining the response height of RI. A secondary carbonization temperature of 800℃ was better. Figure 7 shows a chart when a 15 μl mixture of five carbohydrates, sucrose, glucose, lactose, fructose, and maltose was measured using pure water as the mobile phase and a flow rate of 0.5 cc/min using a differential refractometer. A has a secondary carbonization temperature of 700°C, and B has a secondary carbonization temperature of 800°C. Three peaks were separated for A and three peaks for B. Although only one component was insufficiently separated in B, it seems possible that the measurement conditions could be further selected. Effects of the invention (1) The present invention paved the way for high-pressure carbonization of coal direct liquefaction high-boiling fractions, which have relatively low added value, and use them as high-value added high-performance liquid chromatogram column packing materials. (2) The carbide yield increased at the primary carbonization temperature of 600°C for 2 hours.
It is obtained in a high yield of 29 to 56%, the reduction rate due to secondary carbonization is 5 to 10%, and the yield of column packing material is about 20 to 45% based on the raw material high boiling point fraction. The yield is high compared to the production of other carbon materials (activated carbon, etc.). (3) The substance of the present invention is a polycyclic aromatic and its polar substance,
Effective for separating bases, nitro compounds, and their isomers by liquid chromatography. (4) When pure water is used as a mobile phase as a liquid chromatography packing material, various carbohydrates can be separated and it can be used as an inexpensive industrial bulk high performance liquid chromatography packing material.

[Brief explanation of drawings]

FIG. 1 is a temperature-pressure curve diagram showing the initial pressure of the inert gas for primary carbonization of the high-boiling point fraction of Illinois coal liquefaction and the pressure change while maintaining the carbonization temperature. Figure 2 shows a column using secondary char from the high boiling point part of Illinois coal liquefaction (800°C) as the column packing material, and the mobile phase as methanol:water:(8:
This is a chromatogram of aromatics using 2Vo1) or acetonitrile. (detector UV). Figure 3 shows benzol, naphthalene, and diphenyl 3 according to various secondary carbonization temperatures of Illinois coal liquefaction high boiling point fraction.
Figure 2 is a separation chromatogram of the mixture. (Detector U.
V.). Figure 4 shows benzol, naphthalene and
Figure 3 is a separation chromatogram of a diphenyl 3 mixture. (detector UV). FIG. 5 is a diagram showing the retention times of five types of carbohydrates using Illinois charcoal liquefaction high boiling point secondary carbonization temperature 800°C char as a chromatography filler. (Detector RI). Figure 6 a and b are Illinois coal liquefaction high boiling point fraction secondary carbonization temperature 700℃a, secondary carbonization temperature 800℃b
This is a chromatogram showing the separation performance and quantitative properties of glucose and sucrose. (Detector RI).
FIGS. 7A and 7B are chromatograms of a mixture of five types of carbohydrates using a charcoal column filler having a secondary carbonization temperature of 700°C A and a secondary carbonization temperature of 800°C B of the high boiling point fraction of Illinois coal liquefaction. (Detector RI).

Claims (1)

[Claims] 1. The high boiling point fraction of 350-480℃ of coal direct liquefied oil obtained by high-temperature, high-pressure hydrocracking of coal is heated to an initial pressure of 0-50Kg/cm2 under self-atmosphere gas or inert gas at a temperature of 500℃ or ^higher . The carbide obtained after primary carbonization under pressure is further subjected to secondary carbonization at 600°C to 900°C and an initial pressure of 0 to 10 kg/cm ² under a self-atmosphere gas or an inert gas. Method for producing liquid chromatographic packing material from coal liquefied oil.