JPS59105079A - Treatment of organic material by utilizing hot alkaline water - Google Patents

Abstract

PURPOSE:To recover gas or liquid useful as raw material for fuel or organic synthesis from low-value or waste materials, by placing a mixture of an organic material and a water solution of an alkali at high temperature and pressure so that it may undergo hydrolysis and decarboxylation. CONSTITUTION:A mixture of an organic material such as coal, organic waste such as pulp waste liquor, soil water or sewage sludge, wood, paddy straw and bamboo, and a water solution of an alkali is placed under high temperature and high pressure to cause hydrolysis and decarboxylation. The method accelerates the hydrolysis fo the organic material, addition of hydrogen and hydroxyl group, separation of carbon and oxygen from the organic material in the form of carbon dioxide and increase of the hydrogen content. Liquefaction proceeds without the use of costly hydrogen and composition of the recovered product can be varied by controlling conditions of heating. Thus the condition of reaction may be established according to the aimed product, i.e. 250-350 deg.C for increased yield of oily substance and 400 deg.C for increased yield of natural gas-like gas.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of converting a mixture of various organic materials and an aqueous alkaline solution into a gas or liquid by subjecting the mixture to high temperature and pressure.

By pulverizing various organic particles and turning them into a slurry with an alkaline aqueous solution and treating them under high temperature and high pressure, the hydrolysis reaction of organic substances is promoted, and the carbon and oxygen contained are combined and removed from the organic particles. The purpose is to decompose and liquefy the equipment 81-1 to recover gaseous or oily liquid materials useful as fuel or organic synthesis materials from the waste materials considered to be of low value or waste.

As a conventional method for gasifying coal, there is a so-called water gas production method in which coal and water are converted into a mixed gas of hydrogen and carbon oxide by passing steam through a red-hot coal seam.

Regarding the liquefaction of coal, methods of increasing the liquid component by subjecting a mixed slurry of oil and coal powder to high temperature and high pressure, or by introducing and adding hydrogen gas are being considered.

Is the water gas production method applicable to coal types with a high calorific value? It is difficult to implement it with low calorific coal such as lignite or waste, and conventional methods for coal liquefaction are Hydrogen is added for the purpose of increasing through high temperature and high pressure treatment, or converting it into saturated hydrocarbons, which are oil-soluble components. The problem with this method is that it requires a large amount of oil as a slurry agent, and when hydrogenation is carried out, there is no point in producing fuel oil using hydrogen, which has a high fuel value. This results in high costs.

The present invention promotes the hydrolysis reaction of organic materials by placing a mixed slurry of organic materials and alkaline aqueous solution under high temperature and high pressure, adds hydrogen and hydroxyl groups, and then adds carbon, oxygen 1, hydrogen By separating carbon and oxygen from the organic material in the form of carbon dioxide, the hydrogen content relatively increases in the component ratio. The basic difference between petroleum and coal is the composition ratio of carbon to hydrogen; in anthracite, etc., the molar ratio of carbon to hydrogen is close to 1, while in petroleum, the hydrogen content is twice that. Liquefaction of coal by hydrogenation is a method of increasing the hydrogen composition ratio.

However, to increase the hydrogen content in proportion to the carbon content, the carbon, element, and oxygen in the composition may be removed from the composition as carbon dioxide, resulting in a petroleum-like substance. The present invention in which aliphatic hydrocarbons are produced will be explained by way of examples.

Figure 1 is 120
``-The following shows the yield of a high boiling point oily substance of 100'C or more when 05 pieces of crushed lignite powder are placed in an autoclave with an internal volume of 10 degrees, and 5 degrees of reaction liquid is added to each and heated for 10 minutes while stirring. This is a graph.

The yield of an oily substance was measured by taking the yield of 1 on the vertical axis and the heating temperature on the horizontal axis, and changing the heating temperature for each type of reaction solution. Curve 3 shows the yield at different reaction temperatures when 1 mol of sodium hydroxide, 5°0, is added, and when heated to about 400'C, an oily substance with a weight ratio of more than 6% of the raw material lignite was obtained. It shows. At low temperatures of 200 to 300°C, the reaction is insufficient and oil formation does not proceed sufficiently, and at temperatures above 450°C, a cassification reaction occurs and the yield of oily substances decreases to about 40%.

In curve 4, in addition to the above-mentioned conditions in which 5 cc of sodium hydroxide was added, hydrogen gas was sealed and the pressure was set to 5° KqAa, and then the pigeons were added. In this case, no increase in oily substances due to hydrogenation was observed, and on the contrary, the co-receivables at each heating temperature decreased.

Curve 5 is the result of adding 5 cc of water to 0.5 mm of raw lignite powder, adding 0.185 J' of slaked lime, and then heating to various temperatures. The yield of oil increases with increasing temperature;
The maximum value is reached at 400"C, and the liquefaction rate rises to about 80% because the carbon and oxygen in the lignite are separated as carbon dioxide, react with slaked lime, and are fixed as calzite. This is due to decarboxylation. It also shows the progress of liquefaction due to

In curve 6, in addition to the combination of the conditions of curve 5, hydrogen gas was sealed, and heating was started after increasing the pressure by 5' Q K9/, 1 = j. In this case as well, the yield of oily substances was lower than the results shown in temperature co-curve 5, proving the advantage of the present invention.

Figure 2 shows the decarboxylation and liquefaction of lignite powder taken into an autoclave with an internal volume of 10"cc under the same conditions as in Figure 1. Indicates the conversion rate of gas and liquid in the substance / H. Vertical + t
The conversion rate calculated backward from the residue is taken as Qf+7, and the horizontal axis is 8.
The reaction temperature was set at . The temperature increase rate of 500 minutes and the high temperature holding time of 10 minutes are the same as in FIG.

Curve 9 is the result of adding 5 cc of a 1 molar thorium hydroxide solution, sealing in hydrogen at an initial pressure of 50 and 7 mm, and then causing a heating reaction at a predetermined temperature. Curve 10 shows the heating results after adding 5 cc of 1 molar sodium hydroxide solution. curve 11
Curve 12 is the reaction result under the condition where slaked lime and water were added and hydrogen was sealed at an initial pressure of 50 to -1 when 0.185' of slaked lime and 500 ml of water were added. Curve 13 is the result of adding only 5°0 of water, no alkaline component, and filling hydrogen gas at an initial pressure of 50 and 9%. curve 1
4 shows the reaction results when 500% of water was added, and the decomposition rate was 790% or more, and most of the organic substances other than inorganic components 3 to 5 in the lignite raw material were converted to gas or liquid.

FIG. 3 shows the total amount of gas generated when representative water, sulfur hydroxide, and slaked lime were added and thermally decomposed in the reaction examples shown in FIGS. 1 and 2, according to temperature. The total amount of gas generated is plotted on the vertical axis 15 and the reaction temperature is plotted on the horizontal axis 16 to compare the amount of gas generated depending on the reaction liquid properties and reaction temperatures. Curve 17-2 Lignite powder 0
Curve 18 is the case when 5°0 of water is added to 5°C, curve 18 is when 5°0 of 1 molar sodium hydroxide solution is added, and curve 19 is when 0% slaked lime is added.
．． This is the case when 185° and water 5°0 are added. Gas chromatography analysis revealed that the gas was a mixed gas whose main components were hydrogen, methane, ethane, propane, and butane. The amount of gas generated increases as the heating temperature rises, but as for the component ratio, the content of compounds with fewer carbon atoms increases as the temperature rises; 4. At temperatures above OO°C, hydrogen gas begins to be generated. This means that the water in the reaction solution was directly reduced by the carbon in the coal, and a reaction similar to the water gas generation mechanism started.

The following table shows examples of decomposition experiments of various organic compounds other than lignite. Anisole, acetone, acetic acid, isopropyl alcohol, etc. were each placed in a λ-tocrepe with a molar volume of 4 occ and hydroxylated.
Or, it is the result of thermal decomposition at 400°C and 450°C with addition of 2000% water. Methane, ethane, propane, and hydrogen gas are produced in the same way as when lignite is decomposed. This shows that decomposition reactions occur in the same way with various organic substances other than lignite.

If we infer the effects of industrialization from the experimental examples shown in the table, we can see that
Add 5 cc of alkaline aqueous solution to 0.57 lignite and heat to 400°C.
When heated to 75C0 mixed scum (methane, ethane,
propane) and 04 (boiling power, over 100'C)
can be recovered, so if 1 lignite is processed, 150
It is calculated that 800 nMl of gas and 800 nm of oily substance will be obtained, and a residue of about 3 K9 will be generated. Actually this is 1
Efficiency is further improved by adding light oil with a boiling point below 00°C.

The present invention is based on the discovery that organic substances can be gasified or liquefied by forming them into an aqueous potassium solution (slurry) and keeping them at a high temperature of around 850°C in a closed container. Compared to the hydrogenation method of It is possible to set conditions according to the purpose of increasing the yield of oily substances by heating up to 350"C and increasing the yield of natural scum-like gas by heating to 400"C, and the reaction temperature is also lower than that of conventional coal liquefaction methods. It is advantageous in that it consumes less energy and does not use a creating medium, and is extremely effective in easily converting various organic substances into useful gases and oily substances.

FIG. FIG. 2 is a club diagram showing the conversion rate of lignite into gas and liquid calculated from the reaction residue. Third
The figure is a club diagram showing changes in the total amount of generated gas as the heating temperature changes during lignite treatment.

The names and codes of the main parts are: yield of oily substance 1, curve 4.
5.6.9.10.11.12.13.17.18.1
It is 9th grade.

Fang 1 diagram Spear 2

Claims (1)

[Claims] Examples of organic materials include coal, organic waste such as valve waste fluid, sewage, and sewage sludge, wood, rice straw, bamboo, etc., and a mixture of an alkaline aqueous solution that is exposed to high temperature and pressure to cause a hydrolytic decarboxylation reaction. , a method for treating organic materials using alkaline hot water, which is characterized by converting these organic materials into flammable gases or liquids.