JP2961247B2 - Gasification method for cellulosic biomass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for gasifying cellulosic biomass. INDUSTRIAL APPLICABILITY The present invention is used in fields such as energy production by gasification of wood and the like, waste recovery such as energy recovery and treatment by gasification of solid organic waste.

[0002]

2. Description of the Related Art Generally, a process called gasification uses a dry raw material at a high temperature (800 to 1200 ° C.), a normal pressure (atmospheric pressure to several atmospheric pressures), and uses air, oxygen, and water vapor as an oxidizing agent. It gasifies. On the other hand, cellulosic biomass usually contains a large amount of water, and in particular, organic waste contains a large amount of water.Therefore, a large amount of latent heat of vaporization of water is required for drying the raw material, which is preferable from the viewpoint of energy balance. Absent. JP-A-5-213778, JP-A-8-5920
No. 2, United States Patent 5,
019 and 135 show a method for gasifying cellulosic biomass by maintaining the cellulosic biomass at a high temperature and a high pressure using a hydrogen-activated metal catalyst in the presence of an aqueous medium. The high-pressure process without water evaporation is preferable from the viewpoint of energy balance since latent heat of water evaporation is unnecessary, and is a process suitable for biomass containing a large amount of water. Furthermore, the gasification method in the presence of an aqueous medium is much lower (350-
(400 ° C.), so that the energy efficiency is further improved.

[0003] However, gasification at low temperature has a problem that the reaction rate is slow, so that the amount of catalyst added becomes large, or that only low-concentration organic wastewater can be treated. In addition, when this gasification method is applied to cellulosic biomass, there is no problem in batch operation, but when continuous, the cellulosic biomass is usually in a solid state,
There is a technical problem of injecting solids at high pressure. Furthermore, the reaction intermediate of cellulosic biomass is highly reactive, and the polymerization reaction to produce carbonaceous products occurs competitively. Can cause problems such as blockage of the reaction process.

[0004] In order to solve the technical problem of "handling solids at high pressure", which is one of the above-mentioned problems, solid cellulose-based biomass must be fluidized or solubilized before gasification. Can be solved. JP-A-5-337497 and JP-A-7-24 disclose a method of fluidizing a cellulosic biomass containing water by heating it at 200 ° C. or higher.
No. 6378. In the case of fluidization, solid biomass changes into a slurry having apparent fluidity, and the amount of soluble components in the raw biomass does not always increase. In order to positively solubilize, increasing the amount of the soluble component by adding an alkaline substance seems to be preferable as a pretreatment for gasification. A method of liquefying a cellulosic biomass containing water at a high temperature and a high pressure in the presence of an alkaline substance is disclosed in JP-A-60-2.
No. 62888 and JP-A-61-73793. In the case of liquefaction, the target substance is liquid oil (oil),
It is known that by this reaction, an aqueous solution in which organic substances are dissolved at a high concentration is by-produced. These fluidization or liquefaction,
If used as a solubilization treatment as a pretreatment for gasification,
Since the aqueous solution can be handled at high pressure, the technical problem of "handling solids at high pressure" can be solved.

[0005] Gasification of cellulosic biomass is possible as described above, but it is unclear whether aqueous solutions obtained by solubilizing cellulosic biomass once can be gasified. . Once subjected to heat treatment, the organic matter in the aqueous solution is a mixture of various degradants and polymers of biomass. As will be described in detail in Examples of the present invention, the present inventor has found that an organic substance (aqueous solution) subjected to such heat history can be gasified. Furthermore, when the aqueous solution was gasified, the amount of carbonaceous by-products was small, suggesting that the problem of "poisoning of the catalyst by the carbonaceous product and blocking of the reaction process" could be solved at the same time.

[0006]

An object of the present invention is to provide an industrially advantageous method for gasifying cellulosic biomass.

[0007]

According to the present invention, a cellulosic biomass is reacted with a reaction temperature of 1 in the presence of an aqueous medium.
Water saturation at 50-350 ° C, reaction pressure at reaction temperature
A step of solubilizing while maintaining the vapor pressure or higher, and gasifying the biomass solubilized product by contacting the aqueous solution containing the solubilized product of the cellulosic biomass obtained in this process with a metal catalyst for hydrogen activation . A gasification method for cellulosic biomass, comprising the steps of:

The cellulosic biomass referred to in the present invention includes various substances including cellulose, for example, wood (chips, powder), bark, leaves, bagasse, waste paper, peat, agricultural waste, forest waste, and cellulose. Various organic wastes (eg, organic waste from food industry, organic waste from alcohol production process, municipal waste, organic sludge, etc.)
Etc. are included.

The solubilization step is carried out by reacting the cellulosic biomass in the presence of an aqueous medium, if necessary, using an alkaline substance at a high temperature and a high pressure. As the alkaline substance, various alkaline substances, for example, salts of sodium, potassium, lithium, calcium and the like, carbonates, formate and the like can be used. The amount of the alkaline substance added is 0 based on the dry matter of the raw material.
-100% by weight. As the aqueous medium, water is usually used, and the amount of use is 1 to 100 parts by weight, preferably 3 to 6 parts by weight, per 1 part by weight (absolute dry weight) of the cellulosic bio. For example, in the case of organic waste,
Usually, it is discharged in a state containing 60 to 99% by weight of water, but such a substance can be solubilized as it is.
From the viewpoint of heat balance and handling, the content of the aqueous medium is preferably adjusted to 75 to 85% by weight. The solubilization treatment is performed under a high temperature and a high pressure.
0 to 350 ° C., preferably 200 to 300 [° C., the reaction pressure, in order to suppress the evaporation of the aqueous medium, water at the reaction temperature
Saturated steam pressure or more (for example, 200 ° C. At 16 atm,
At 300 ° C., 88 atm or more) is employed. The reaction time depends on the reaction temperature, the reactivity of the raw materials, the amount of addition of the alkaline substance, and the like.

In the gasification step, an aqueous solution containing the solubilized cellulosic biomass obtained in the solubilization step is treated with water.
The reaction is carried out by maintaining the catalyst at a high temperature and a high pressure in the presence of a catalyst for elemental activation . Examples of the metal catalyst for hydrogen activation include ordinary industrial nickel, cobalt, molybdenum,
Various metal catalysts for activating hydrogen, such as copper, tungsten, platinum, and iron, can be used. The gasification reaction temperature is 30
The reaction pressure is set at 0 to 450 ° C. or higher than the saturated vapor pressure of water at the reaction temperature in order to suppress the evaporation of water . Since water becomes a supercritical fluid at a reaction temperature of 374 ° C. or higher, a reaction pressure of 226 atm or more is adopted as the reaction pressure in this case. The reaction time depends on the reaction temperature, the concentration of organic substances in the obtained solubilized aqueous solution and the amount of treatment (ratio to the amount of the metal catalyst for hydrogen activation ), and the like. Is preferably in the range of 5 to 180 minutes.

Next, the present invention will be specifically described with reference to the drawings. However, the present invention is not limited to these.

FIG. 1 shows an example of a flow sheet for carrying out the present invention. Reference numeral 1 denotes a solubilization apparatus, and raw materials are supplied through a line 8. Note that this flow sheet does not include a raw material adjustment step, but if adjustment of water content or the like is necessary, the adjustment is performed in advance. The alkaline substance is simultaneously supplied to the solubilization apparatus 1 through the line 9. The heating of the solubilization apparatus 1 is performed by a heating medium,
After heating the solubilization apparatus 1, the heat medium is recovered through a line 25. Examples of the type of the solubilizing apparatus include a heat exchange type screw feeder type apparatus as disclosed in JP-A-62-225586 and a semi-continuous type apparatus as disclosed in JP-A-7-246378. Can be used, but there is no particular limitation. The solubilized product is withdrawn via line 10 and sent to the second solid-liquid separator. In the solid-liquid separation device 2, the product subjected to the solubilization treatment is separated into a solid product and an aqueous solution, and the solid product is withdrawn via a line 11, while the aqueous solution is withdrawn via a line 12. . The type of the solid-liquid separation device 2 depends on the solid-liquid separation property of the product subjected to the solubilization treatment, and the solid-liquid separation property of the product subjected to the heat treatment depends on the reaction conditions. When solid-liquid separation is good, separation can be performed by a simple method such as gravity separation (static separation). On the other hand, when solid-liquid separation is not good, separation methods such as belt press and centrifugation are used. Is adopted. Line 1
The solid product extracted from 1 is of value as a solid fuel because of its low moisture content and can be used as part of the energy source of the process. That is, the solid product can be used as a heat source required for the solubilization treatment and / or a heat source required for the gasification treatment described later. The aqueous solution withdrawn from the line 12 is pressurized by the pressure pump 3 and sent to the gasification reactor 4 via the line 13. Heating of the gasification reactor 4 is performed with a heating medium,
The heating medium is supplied through a line 19. Further line 2
The heat medium recovered via the heat exchanger 0 can be used for preheating the gasification reactor 4. The heat medium recovered via the line 23 can be further used for heating the solubilization apparatus 1, and supplies the insufficient amount of heat via the line 24. The inside of the gasification reaction device 4 is packed with a catalyst, and is gasified by a catalytic action. The gasification product gasified by the gasification reactor 4 is withdrawn via the line 14 and sent to the cooler 5. The cooler 5 is cooled by supplying a heating medium or cooling water from a line 21, and the recovered heating medium or cooling water is recovered via a line 22.
The recovered heat medium or hot water can be used for preheating the gasification treatment device 4 or heating the solubilization treatment device 1.
The cooled gasification product is sent through line 15 to a pressure reducing valve at 6, where it is depressurized to atmospheric pressure. The decompressed gasification product is sent to a gas-liquid separator 7 through a line 16. In the gas-liquid separator 7, the gas product and the treated aqueous solution are separated, and the gas product is recovered via a line 17, and the processed aqueous solution is recovered via a line 18. The gaseous products are used as gaseous fuels or chemical raw materials, while the treated aqueous solution undergoes further treatment such as wastewater treatment. Part of the treated aqueous solution can also be used for adjusting the water content of the raw material.

This process is described in Japanese Patent Application Laid-Open No. 9-241001.
It is also possible to adopt a device equipped with a gas-liquid separation function in the gasification reactor as shown in the above item, and in this case, it is expected that gasification efficiency can be improved and hydrogen can be selectively produced. Is done. Further, a high-pressure gas-liquid separation device can be employed between the cooler 5 and the pressure reducing valve 6, and in this case, it is expected that high-concentration hydrogen and methane can be recovered from the difference in gas solubility. . Also, Japanese Patent Application Laid-Open No. 9-2553
As shown in No. 03, it is also possible to use solar heat for all or part of the heat required for the process,
In this case, it is expected that all or most of the obtained gaseous products can be effectively used. In any case, the flow sheet of FIG. 1 is an example of an embodiment of the present invention, and the present invention is not limited to this.

[0014]

The present invention proposes a new basic process for gasifying water-containing cellulosic biomass. Usually, cellulosic biomass is solid,
Handling under high temperature and high pressure conditions is difficult, and this is a major factor that makes it difficult to commercialize the gasification reaction. According to the present invention, it is possible to solve the handling problem by employing the solubilization treatment step,
The gasification reaction can be put to practical use. Furthermore, when an aqueous solution containing a solubilized product of cellulosic biomass is used as a raw material, the polymerization reaction, which is a side reaction, is small, and almost no carbonaceous product is generated. Can be solved at the same time.

[0015]

Next, the present invention will be described in more detail with reference to examples. In this example, a commercially available microcrystalline cellulose was used as a model substance of cellulosic biomass, and a commercially available industrial nickel catalyst (reduced with hydrogen before use) was used as a hydrogen activating metal catalyst.

Example 1 To confirm whether a product (an aqueous solution containing a biomass solubilized product) once subjected to a heat treatment (thermal history) can be gasified, 5 g of cellulose was added to 30 ml of water, and sodium carbonate was used as an alkaline substance. The mixture was mixed with 0.25 g and first subjected to a solubilization treatment in a batch-type pressurized reaction vessel. After pressurizing to 30 atm with nitrogen gas in advance to suppress the evaporation of water,
It was heated to 300 ° C. at a rate of about 10 ° C./min in an electric furnace, and kept at this temperature for 30 minutes. In this case, the reaction pressure was kept above the saturated vapor pressure of water. After cooling and reducing the pressure, the solubilized product was taken out. The solubilized product had very good solid-liquid separation properties, and a tar-like solid was separated at the bottom of the pressurized reaction vessel, and a yellow-brown transparent aqueous solution was separated above the pressurized reaction vessel. About 32 g of the aqueous solution was recovered and had a property of a total organic carbon concentration (TOC) of 22,000 pm and a pH of 4. The tar-like solid weighs about 1.5 g and has a carbon content of 7
3% by weight, hydrogen content 7% by weight, oxygen content 20% by weight, high calorific value (calculated by Dulong formula) 31k
It had a calorific value of J / g, comparable to that of coal, and was usable as a solid fuel. The obtained aqueous solution was mixed with 1 g of a nickel catalyst, and mixed in the same batch-type pressurized reaction vessel.
It was gasified. In order to suppress the evaporation of water, the pressure was previously increased to 30 atm with nitrogen gas, and then heated to 350 ° C at a rate of about 10 ° C / min in an electric furnace, and cooled immediately when the temperature was reached. In this case, the reaction pressure was kept above the saturated vapor pressure of water. After cooling, the product gas was collected and analyzed by gas chromatography. Further, the treatment aqueous solution and the catalyst were recovered. Generated gas (excluding pre-pressurized nitrogen gas)
Is a gas mainly composed of hydrogen and carbon dioxide, about 1 g (60
mmol). The gas composition was 55% by volume of hydrogen, 34% by volume of carbon dioxide, 10% by volume of methane, and 1% by volume of a hydrocarbon gas having 2 or more carbon atoms. The gasification rate was about 50% on a carbon basis. Treatment solution is TOC5600pp
m, pH7, TOC removal rate 75%
Met. The remaining 25% of the carbon was dissolved as inorganic carbon (such as dissolved carbon dioxide) in the treatment aqueous solution. Furthermore, the recovered catalyst had almost no precipitation of tar or carbonaceous products. These results show that the aqueous solution obtained by once heat-treating and solubilizing the cellulosic biomass can be gasified using a hydrogen-activated metal catalyst. This indicates that almost no by-products may be formed, which may cause the following.

[Brief description of the drawings]

FIG. 1 is an example of a flow sheet for implementing the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Solubilization apparatus 2 Solid-liquid separator 3 Press-in pump 4 Gasification reactor 5 Cooler 6 Pressure reducing valve 7 Gas-liquid separator

Claims (3)

(57) [Claims] 1. A method for preparing a cellulosic biomass in the presence of an aqueous medium at a reaction temperature of 150 to 350 ° C. and a reaction pressure of the reaction temperature.
And carrying out a solubilization treatment while maintaining the saturated vapor pressure of water at or above the water level , and contacting the aqueous solution containing the solubilized product of the cellulosic biomass obtained in this step with a metal catalyst for hydrogen activation to thereby remove the biomass. A method for gasifying a cellulosic biomass, comprising the step of gasifying a solubilized product. 2. The method according to claim 1, wherein the solubilizing step further comprises adding
The cell according to claim 1, wherein a substance is present.
Gasification method of loin biomass. 3. A solid by-product obtained in the solubilization step.
Heat source and / or gas required in the step of solubilization
Use as a heat source required for the process
3. The gasification method for cellulosic biomass according to 1 or 2.