JPS5936191A - Method for treating carbonaceous material - Google Patents

Abstract

PURPOSE:To obtain a hydrocarbon liquid and a gas suitable for chemical raw materials and fuels, by dispersing a fine powdery carbonaceous material in a preheated hydrogen stream, hydrogenating and decomposing the carbonaceous material under specific conditions, and reacting the decomposition product in the presence of steam. CONSTITUTION:A previously pressurized hydrogen is heated in a preheater 2 and introduced into a reactor 3. A fine powdery carbonaceous material is fed from a feeding apparatus 1 and dispersed in the hydrogen stream to react, hydrogenate and decompose the fine powdery carbonaceous material at 500- 1,000 deg.C and for 0.01-10sec. Steam is then introduced into the reaction gas to give 10-70% volume ratio thereof, and the reaction is continued at 500-1,000 deg.C for further 2-60sec. The reaction product is then cooled to >=600 deg.C to separate solid char and give the aimed gaseous and liquid product. EFFECT:The yield of benzene, toluene, xylene, ethane, etc. is particularly improved, and the formation of methane is suppressed.

Description

[Detailed description of the invention]

The present invention relates to a method for processing carbonaceous materials with hydrogen to produce hydrocarbon liquids and gases suitable as chemical feedstocks and fuels. More specifically, by reacting a solid powdery carbonaceous material such as coal with heated hydrogen and then further reacting it in the coexistence of water vapor, hydrocarbon liquids and gases can be produced in high yields as chemical raw materials and fuels. The present invention relates to a method for treating carbonaceous raw materials produced by. Various methods are generally known for producing hydrocarbon liquids and gases suitable as chemical feedstocks and fuels from carbonaceous materials such as coal. One such method is US Patent 3. θ3θ, No. 292, dry coal particles in a hydrogen stream at a total pressure of about 50θ to θθθpsig,
A process is described that involves heating to a range of 0 to 0 to steam θθθ−°C. In this method, hydrogen and coal particles are mixed and the mixture is heated from the outside to substantially gtθ~6θθ℃.
However, because this requires a relatively long reaction time of several seconds to minutes, some of the 2-decomposition products undergo further hydrogenolysis, and in particular, the production of methane increases significantly7. This has the disadvantage that the hydrogen consumption rate increases. In addition, the applicant of the above patent, R.Filburn C. Schroeder, wrote in Japanese Patent Application Laid-open No. 30-75202,
Water vapor is made to coexist in a gas stream of hydrogen and carbon monoxide, and coal particles are introduced into the gas, /, θθθ ~ ta, θθθpsi
It states that by heating the coal to a pressure of 730'F or higher, hydrogen cracking of one coal and hydrogen production through a reforming reaction are performed simultaneously. However, this method has the disadvantage that the hydrogen partial pressure, which is important in the initial decomposition of coal, is reduced by the addition of steam, and the carbonization reaction by condensation polymerization that proceeds simultaneously with thermal decomposition is not suppressed, resulting in a decrease in the yield of useful liquefied products. be. On the other hand, in JP-A No. 3/3.21, 0.9, granular coal is introduced into a hydrogen stream heated to /, θθθ~/, g, tθ°C, and a substantial to lθθ~/, Oj
A reaction process with a reaction temperature of 0° C. and a short time period of 0.02 to 7 seconds is described. Since this method is a short-time coal hydrogenolysis method that involves rapid heating to high temperatures, the product is mainly a relatively neutral hydrocarbon liquid, and is not a chemical raw material or a high value-added product. Further secondary treatment processes are required to obtain light fuels. The present inventors have developed a method for hydrogenolyzing carbonaceous materials such as coal and making it suitable for use as a useful chemical raw material and fuel.

[7] The result of extensive research to overcome the following drawbacks in producing hydrocarbon liquids and gases. (Al Adding and dispersing a powdered carbonaceous material such as pulverized t7 coal into a hydrogen stream that has been preheated to a predetermined temperature (b)
After hydrogenolyzing the powdery carbonaceous material for 0.07 to 10 seconds at a temperature range of 0.0 to 0.0 °C, (e) water vapor is introduced into the reaction gas at a volume ratio of 10 to 70%. and further λ in the temperature range of joo~/,000℃
By continuing the reaction for ~60 seconds, we have found an economical method to produce high yields of hydrocarbon liquids and gases suitable for useful chemical feedstocks and fuels, while at the same time reducing the hydrogen consumption rate. be. That is, according to the present invention, there is provided a first reaction zone in which pre-pressurized hydrogen is heated and pulverized coal particles are introduced into the gas stream to rapidly thermally decompose the coal particles; Water vapor is introduced into the gas mixture so that the volume ratio becomes 70 to 7θ%, preferably 0% to 0%, and the mixture is further heated for 2 to 60 seconds, preferably. By providing a second reaction zone that performs the hydrogenolysis reaction for ~λθ seconds, the yield of useful chemical raw materials, especially benzene, toluene, xylene, and ethane, etc. is improved, and at the same time, the production of methane is suppressed. and hydrogenation of carbon dioxide produced by decomposition of coal (formula (1,1), - methanation of carbon oxide (formula (2))% formula%) (2) and the following formula (3) C+t by (4)
120 C: 0 + 112 (3) Co
+I+20-→co, +H2 (41) By performing hydrogen production, it is possible to reduce the apparent consumption rate of hydrogen and improve economic efficiency. It is necessary to maintain a high hydrogen partial pressure in order to increase the decomposition yield in the thermal decomposition of hydrogen, and in order to economically obtain useful products by decomposing the next product, it is necessary to coexist with water vapor. We have discovered that this is effective, and have made it possible to perform this simultaneously in the same reaction system [7].The present invention combines a hydrogen cracking reaction by rapid heating of coal and a secondary cracking reaction by introducing steam It is a continuous area,
In addition, in order to limit the reaction time in each region, the reactor type is preferably a parallel flow type, for example, from one end of the reaction tube. Preheated hydrogen and coal particles are supplied, and when the residence time has elapsed, superheated steam is introduced at a predetermined rate from the side pipe, and when the predetermined reaction time has elapsed, the reaction is started. It can be designed to reach the outlet of the pipe. Notwithstanding the foregoing, it goes without saying that all reactors that can satisfy the method and conditions of the present invention are included in the present invention. According to the present invention, in order to heat the coal to a predetermined temperature and start the reaction, part or all of the introduced hydrogen is preheated in advance. The method may be conventional heater heating, partial combustion of introduced hydrogen, or a combination thereof. The reaction temperature between heated hydrogen and coal particles is 00~/, 0θθ
The temperature is preferably 600 - θO<0>C. At high temperatures, the decomposition into methane progresses, and at low temperatures, the coal reaction proceeds ■7. The introduction ratio of hydrogen to coal is 0. The range of / : / to / : / is good. Coal feed gills. The hydrogen preheating temperature is determined by taking into consideration the reaction temperature and other factors. The hydrogen used in the final process may be from any industrial source, e.g. char and/or coal gasification, naphtha and/or methane reforming, and may be partially contaminated with methane, carbon oxides, etc. , the carbonaceous materials used include coal, lignite, etc. I Coal, peat, oil shale, tar sands. Such as tar pitch. If these are supplied in solid form, dry them in advance and
0 micron or less, preferably 100 micron or less (/j
Use by crushing to 0 mesh or less. It is also possible to use a catalyst effective for hydrogenolysis of these carbonaceous materials. According to the present invention, after the decomposition reaction of coal particles is carried out in the aforementioned reaction gas consisting essentially of hydrogen, water vapor is introduced into the mixed gas and the reaction is further continued. The reaction temperature is preferably in the range of 500 to 1000℃, especially θ0 to 90θ℃, and the steam is superheated to maintain the temperature IW.
It can also be used as Further, part or all of the water vapor to be added can also be introduced as water. The reaction pressure is 70 to 200 steps, preferably 3θ to /θθ, and the reaction time is 0.07 to /θ seconds, preferably 0.7 to 2 seconds in the first reaction zone under hydrogen atmosphere. , 2 to 60 seconds in the second reaction zone with added steam, preferably j-2θ seconds, depending on the type of carbonaceous material in the feedstock and the type of product desired. For example, gaseous products such as ethane or benzene,
The optimum value can be selected depending on whether a light liquid product such as toluene or xylene is intended. The products of the reaction include gaseous and liquid conversion products of coal, as well as unreacted coal, char, and hydrogen. The reaction product from the λ-th reaction zone is produced at a temperature below 60θ°C, preferably y! It is cooled to below Oθ°C. This method can use existing indirect heat exchangers, water sprays and coolants such as gases such as cryogenic hydrogen or various hydrocarbon liquids. EXAMPLES The present invention will be explained in detail by showing Examples and Comparative Examples below. Note that this example shows one embodiment of the present invention, and the present invention is not limited thereto. Examples/Next I: Lignite having the composition shown was ground to a size of 100 mesh or larger, dried and used. Composition (dry basis) C: j 5'ichi I]: ¥, % N: (7,9% S: 3.3% 0: 2θ, 2 ash content: / /, g% Heated to ♂θθ℃ θ per Kq of coal/Kq
, tKq, were continuously supplied from the second part of a reaction tube with an electric heater having an inner diameter of 22 mm and a length of 3 meters. (See Figure 1) Reaction temperature, l! After 7 seconds of reaction time under the conditions of 00℃ and reaction pressure cuff 0, heat the superheated stino from the side tube of 1 reaction tube to a warped color; the partial pressure of steam in the gas should be 20 degrees ( The reaction was continued for another 6 seconds at the same temperature as the addition of 2. After the product was rapidly cooled to 90°C and the solid char was separated, the gaseous and liquid products were collected and analyzed, and the following results were obtained. Reaction yield (anhydrous ash-free tea) Methane 72% Nitane / θ CH COB CH GO2/2 Superior benzene H I Toluene / Related light oil (B, P, (g O θ ℃) / TA hydrogen consumption 2. Comparative example/ Using the same coal and the same reaction apparatus as in the example,
Conducted without introducing steam [7]. The reaction conditions were /θθ℃, reaction time of yAyl-7 seconds at 2θ,
Other conditions are the same as in the example. The results are shown below. Reaction yield (anhydrous and ash-free basis) Methane 2. ! ? Chetan CO/, : 2% CO200, 5-benzene 7 Titoluene 0.7 light oil (B, P, (Oθ℃) Hydrogen consumption rate
Evening, otsuchi

[Brief explanation of drawings]

FIG. 1 is a block flow diagram showing an example of an apparatus for carrying out the method of the present invention. 1 Coal feeder 2 Hydrogen heater 3 Reactor 4 Char separator 5 Cooler 6 Liquid product recovery device Patent applicant Asahi Kasei Corporation

Claims (3)

[Claims] (1) In a processing method for producing hydrocarbon liquid and gas by hydrogenating a powdery carbonaceous material, (a) adding and dispersing a finely divided powdery carbonaceous material into a preheated hydrogen gas stream (b) ) O9θ/~/ in the temperature range of tθθ~/θθθ℃
After hydrogenolyzing the powdered carbonaceous material for θ seconds, (C) water vapor is introduced into the reaction gas so that the volume ratio becomes 7θ to 2θ percent, and further heated for 2 to 20 seconds in a temperature range of 500 to 7000°C. A method for treating carbonaceous materials characterized by continuing the reaction for 60 seconds (2) A method for treating a carbonaceous material according to claim 7, wherein the powdery carbonaceous material is coal with a size of about 500 microns or less. (3) A method for treating a carbonaceous material according to claim 7, characterized in that the reaction pressure is /θ to 200 Kf/i.