JP6891706B2 - Hydrogen production method using biomass resources - Google Patents

Description

The present invention relates to a method for producing hydrogen using biomass resources such as wood waste in the palm palm industry.

Palm coconuts can be cultivated for the purpose of producing fats and oils from the pulp of fresh fruit bunches (FFB: Fresh Fruit Bunch) and palm coconut kernels, respectively. The amount of fats and oils obtained per unit area of palm palm is extremely large among plants, and large-scale cultivation (plantation agriculture) is carried out as a commercial crop, especially in Indonesia and Malaysia.

Fruits harvested from palm palms, which are cultivated on a large scale industrially today, are used in the production of soaps and edible vegetable oils. Palm oil is obtained from the flesh (pericarp) of the fruits of the fresh fruit bunch (FFB), and palm kernel oil is obtained from the palm kernel in the center. The quality of palm oil and palm kernel oil are different. Palm oil is mainly used for cooking, and palm kernel oil is mainly used for processed foods. In recent years, palm oil and palm kernel oil have been used as biomass fuels. Is being used as a substitute for diesel fuel.

As a biomass fuel, in recent years, palm coconut shell (PKS: Palm Kernel Shell) obtained as a by-product when palm oil of palm coconut or palm kernel oil is collected has been used. In particular, recently, the supply of thinned wood, which is a biomass resource, has tended to be insufficient, and the amount of palm coconut shell (PKS) used has been increasing.

In the palm oil industry, which collects palm oil and palm kernel oil from palm palms, in addition to the above-mentioned palm palm shells (PKS), empty fruit bunches (EFB: Empty Fruit Bunch) and old palm trees (OPT: Oil Palm Trunk) , Palm branches and leaves (OPF: Oil Palm Front) and the like are generated as by-products. In addition, when oil is squeezed from the fruits of a fresh fruit bunch (FFB: Fresh Fruit Bunch), a large amount of palm coconut wastewater (POME: Paim Oil Mill Effect) containing organic substances such as oil is generated.

Here, since the empty fruit bunch (EFB) is steamed when the fruit is collected from the fresh fruit bunch (FFB: Fresh Fuel Bunch) of palm palm, the water content of the empty fruit bunch (EFB) is generated by the steam at this time. Is 65% or more, so it is not suitable as a fuel for combustion. For this reason, most of the empty fruit bunches (EFB) are returned to the farm and discarded, but some are burned in a boiler together with palm fiber (Fiber) and palm coconut shell (PKS), and the burned ash is used as fertilizer. It's being used.

There is a need to facilitate the storage and transportation of renewable energy obtained from such unused biomass resources derived from the palm industry. For example, methane is produced by fermenting the juice of old palm tree (OPT) to produce methane and bioethanol, and by treating oil-containing wastewater (POME) generated when oil-water separation is performed when producing palm oil. The case of gaining has begun.

Japanese Patent No. 4065960 Japanese Patent No. 4418871 Japanese Patent No. 4665257

However, there is a problem that the range of use of methane and bioethanol obtained by using renewable energy from unused biomass resources derived from the palm industry is limited as they are. Methane is a typical greenhouse gas, and if it is in its original form, it may have an adverse effect on the environment. In addition, bioethanol can be used only for limited purposes such as automobiles equipped with an ethanol engine. Therefore, it is desired to reform the hydrogen into hydrogen, which has a wider range of industrial use than methane and bioethanol and has no risk of adversely affecting the environment.

The present invention has been made in view of the above-mentioned circumstances, and methane and bioethanol obtained by using renewable energy from unused biomass resources derived from the palm industry can be carbonized without consuming external energy. It is an object of the present invention to provide a method for producing hydrogen using a biomass resource that can be reformed into hydrogen in neutral.

In order to solve the above problems, the hydrogen production method using the biomass resource of the present invention includes a palm oil production process for obtaining palm oil from palm palm trees, a separation process for obtaining recycled raw materials from palm palm trees, and the above. A semi-carbonation process that produces biomass semi-carbohydrate and bioethanol from recycled raw materials, and a hydrogen production process that produces methane using the emissions produced in the palm oil production process and obtains hydrogen by steam reforming together with the bioethanol. The hydrogen production process is characterized in that the regenerated energy generated by using the emissions generated in the palm oil production process is used as an operating energy source.

According to the method for producing hydrogen using the biomass resource of the present invention, palm branches and leaves (OPF), palm old trees (OPT), empty fruit bunches (EFB), and palms that have been simply incinerated have not been effectively used in the past. Recycled raw materials such as coconut shell (PKS) and palm fiber (Fiber) and emissions from the palm oil production process are used to produce methane and biomass, and surplus energy is used to generate steam. Since hydrogen is generated by steam reforming from palm oil, it is possible to obtain hydrogen at extremely low cost without newly supplying raw materials and energy from the outside. By reusing unused waste generated in the palm palm industry without discharging it as waste, it is possible to purify wastewater and suppress the generation of greenhouse gases. It can contribute to sustainable operation.

Further, in the present invention, the sorting process comprises a harvesting step of separating and harvesting fruit bunches and palm branches and leaves growing around the fruit bunches from palm palm trees, respectively, and the semi-carbonization process squeezes the palm branches and leaves. A squeezing step of separating into a squeezed liquid and a first solid residue, a bioethanol production step of fermenting the squeezed liquid to produce bioethanol, and a semi-carbonizing of the first solid residue to obtain a biomass semi-carbohydrate. The palm oil production process comprises a carbonization step, in which the fruit is degreased from the fruit bunch and separated into the fruit and the empty fruit bunch after defruiting, and the fruit is squeezed and coarse palm is used. The hydrogen production process comprises an oil squeezing step of separating into oil and a second solid residue, and an oil-water separation step of adding water to the crude palm oil, suspending the mixture, and then separating the oil and water to obtain palm oil and separated water. Is a first gasification step of gasifying the bioethanol, a methane production step of fermenting the separated water to produce methane, and a palm coconut shell and the second solid residue obtained in the oil extraction step. An energy generation step that generates water vapor, electric power, and heat energy from palm fibers, and a steam reformer that generates hydrogen by a steam reforming method from the bioethanol gas, the methane, and the water vapor obtained in the energy generation step. It is characterized by having a quality hydrogen production process.

Further, in the present invention, the steam reforming hydrogen production step is a reaction step of reacting the bioethanol gas and the methane with the steam, and separation of hydrogen generated by the reaction step and carbon monoxide and carbon dioxide. It is characterized by including at least a step.

Further, the present invention is characterized in that the semi-carbonized process further includes a compression molding step of compression molding the biomass semi-carbide to pelletize it to obtain a solid biomass fuel.

Further, in the present invention, a lignite drying step of drying lignite, a lignite crushing step of crushing the dried lignite to obtain lignite powder, and a second gasification step of generating carbon monoxide from the lignite powder. It is characterized by further comprising a biomass reformed coal production process including the above, and further adding the carbon monoxide to the steam reformed hydrogen production step.

Further, the present invention is characterized in that the electric power or thermal energy obtained in the energy generation step is used as an operating energy source in the steam reforming hydrogen generation step.

Further, the present invention is characterized in that the hydrogen production process further includes a water electrolysis hydrogen production step of generating hydrogen by a water electrolysis method of electrolyzing water using the electric power obtained in the energy generation step. ..

Further, the present invention is characterized in that, as the palm branch and leaf, a petiole is used among the leaf portion on which the palm leaf grows and the petiole forming the fruit bunch side of the leaf portion.

Further, the present invention is characterized in that, in addition to the palm branches and leaves, the trunk of the palm palm tree is further supplied to the juice squeezing step.

According to the present invention, a biomass resource capable of reforming methane or bioethanol obtained by using renewable energy from an unused portion of palm palm into hydrogen in carbon neutral without consuming external energy is used. It is possible to provide a method for producing the present hydrogen.

It is a block diagram which showed the outline of the hydrogen production method using the biomass resource of this invention. It is the schematic explanatory drawing which showed typically the method of producing hydrogen using the biomass resource of this invention. It is a flowchart which showed the hydrogen production method using the biomass resource of this invention step by step. It is explanatory drawing which shows each component part of the palm palm. It is a schematic diagram which shows the palm branch and leaf of the palm palm. It is a schematic diagram which shows the cross section of the fruit of a palm palm.

First, the technical background of the present invention will be described.
As a method of using renewable energy, Power to Gas (PTG) is a technology for converting a large amount of surplus electricity obtained from renewable energy into hydrogen or methane, and storing and transporting it. Here, renewable energy is energy whose energy source is constantly regenerated by natural activities, is supplied semi-permanently, and can be used continuously, and is a new energy (small and medium-sized hydraulic power) that replaces fossil fuels, which are finite resources.・ It means energy such as geothermal energy, solar power, solar heat, wind power, snow and ice heat, temperature difference, biomass, etc.), large-scale hydraulic power, wave power, ocean temperature difference heat, etc. Renewable energy still has issues such as energy conversion efficiency, cost, and supply-demand balance, but since it can obtain energy without emitting greenhouse gases, it is regarded as important as one of the measures against global warming. There is.

In the field of renewable energy, one of the most urgent obligations is to solve the challenge of storing electricity from fluctuating energy resources such as the sun and wind. The PTG technology concept described above has evolved as a very promising initiative. There are numerous projects around the world, some of which have completed the pilot phase and are heading for commercial operation. The principle of PTG technology is quite simple, the power from renewable energy is used to electrically break down water into hydrogen and oxygen.

The obtained hydrogen can be converted into electricity or used directly as fuel. The conversion of electricity to hydrogen has some energy loss, but is effective for one purpose. Electricity from renewable energy can be stored as energy-rich hydrogen, and methane gas can be obtained from carbon if necessary. Existing gas infrastructure is available for transportation and storage to some extent.

For example, the world's largest methanation facility with a maximum production capacity of 6 MW has been in operation since mid-2013 in Werlte, northern Germany. At the facility, German car maker Audi is helping to convert 110,000 tonnes of slurry and food waste annually instead of water into methane. The energy required for the methanation process uses excess electricity generated at offshore wind farms in the North Sea.

Audi is also building a facility to convert carbon dioxide, a component of the gas produced by the biogas facility, into methane. The biogas facility itself is a facility of EWE, a local utility company, and it is said that raw materials for operating the facility can be obtained from within a radius of 150 km. The facility converts organic matter into biogas, which consists of about two-thirds of methane and one-third of carbon dioxide. Then, carbon dioxide is removed from the biogas obtained through a number of processes by passing it through activated carbon that adsorbs carbon dioxide. In the next stage, carbon dioxide is desorbed at low pressure and sent to the methanization facility. Then, methane is produced from hydrogen by the process of _{CO 2} + 4H ₂ → CH ₄ + 2H _{2 O.}

Other existing technologies for PTG include gas liquefaction (GTL), biomass liquefaction (BTL), coal liquefaction (CTL), dimethyl ether (DME), and alternative natural gas (SNG).

Of these, biomass liquefaction (BTL) is an abbreviation for "Biomass To Liquid" and refers to fuel produced by liquefying biomass (biological resources). Organic substances such as wood are heated into gas, and liquid fuel is synthesized from hydrogen and carbon monoxide contained therein. It is characterized by being able to use almost all organic substances such as wood, paper, waste plastic, food waste, and sludge as raw materials.
In addition to not competing with food, BTL has advantages such as (1) it can be widely used as fuel for automobiles and boilers, (2) it produces less sulfur even when burned, and (3) it is easy to store because it is a liquid. However, mass production technology has become an obstacle and has not been widely used.

Traditionally, biofuels have been preceded by the use of bioethanol, which ferments sugar cane and corn. In Japan, a demonstration project to mix and sell gasoline at a gas station started in 2007, and the government has set a goal of covering 3% of gasoline demand by 2020 in the basic energy plan before the Great East Japan Earthquake. However, most of them are imported from Brazil, and it is said that there are many problems in securing stability.

Next to bioethanol is biodiesel fuel made from rapeseed and sunflower seeds. Europe, which has a high penetration rate of diesel vehicles, is leading the way in technological development, but there are limits to the amount of raw material plants that can be produced, and it is said that there are many issues in securing stable biodiesel fuel.

On the other hand, hydrogen energy can be produced from a wide range of energy sources, and because it produces only water when burned, it is expected to be a secondary energy used in energy systems in a sustainable society, and various technological developments have been made. Is underway.

In producing hydrogen from primary energy, hydrogen production from existing fossil fuels and nuclear energy can be done relatively easily by using fuel reforming and large-scale electrolysis of water, but solar energy, which is a renewable energy, Hydrogen production from wind energy is not always cheap and efficient due to its small scale and fluctuations in energy output.

On the other hand, biomass has the advantage of being able to produce hydrogen relatively stably among renewable energies because it can perform stable energy conversion as renewable energy. Currently, renewable energy accounts for only 1% of the primary energy supply in Japan, but most of it is supplied by biomass, and hydrogen production from biomass has a large impact on renewable hydrogen. Expected as a source.

In order to produce hydrogen from biomass, the method of gasifying the biomass and reforming the generated flammable gas is most often used. The gas produced by gasification of biomass varies depending on the gasification method, but mainly contains some of hydrogen, methane, carbon monoxide, and carbon dioxide as main components. The production of hydrogen by reforming methane is due to the following reaction.
(1) CH ₄ + H ₂ O → 3H ₂ + CO
(2) CO + H ₂ O → H ₂ + CO ₂
Since methane can be easily converted into hydrogen and carbon dioxide by such a reaction, it is not difficult to obtain hydrogen if it can be converted into a gas form. Therefore, in order to obtain hydrogen from biomass, it is important how to efficiently gasify it. Compared to the reforming of generated gas, the biomass gasification technology itself has development issues, and much research is underway.

Typical biomass gasification technologies are roughly divided into thermochemical gasification and biochemical gasification. The former is to heat biomass to promote chemical reactions such as thermal decomposition, partial oxidation, and hydrolysis, and has the characteristic that gasification proceeds quickly and relatively completely. High temperature gasification and supercritical water gasification correspond.
The latter involves the action of microorganisms on biomass to promote conversion to gas by the action of fermentation. It takes time because it is a biological action, and complete gasification is difficult, but it can be realized under relatively mild conditions. Has advantages. Methane fermentation and hydrogen fermentation are applicable.

On the other hand, coal can also be used for hydrogen production. Compared to other fossil fuels, coal has a long recoverable life and is widely distributed all over the world. It has the characteristics of high supply stability and excellent economic efficiency. On the other hand, about half of the finite recoverable reserves are low-grade coal represented by lignite, which is rarely used. Using such coal, metanation technology development under high-concentration CO conditions and calorie-enhancing technology for alternative natural gas (SNG) have been developed. As a result, low-grade coal such as lignite can be converted into SNG (methane, ethane, propane, etc.), which is more efficient and more convenient than the existing gasified technology, and the low-grade coal can be effectively used. ing.

An example of hydrogen production is the steam reforming method. However, since steam reforming using natural gas or naphtha is a large endothermic reaction, it requires a high temperature of 900 ° C or higher, which is harsh for catalysts and reforming pipes. In addition, excess water vapor is used to prevent the combustion of a large amount of raw material hydrocarbons and the precipitation of carbonaceous substances on the catalyst in order to maintain the reaction temperature, which consumes an extremely large amount of energy. Furthermore, a large amount of carbon dioxide as a reaction and combustion product and nitrogen oxides generated during combustion are released. For example, when natural gas is used as a raw material, the amount of carbon dioxide emitted as flue gas reaches about 0.9 kg per _{1 m 3 of hydrogen.} Hydrogen as a clean energy is in the limelight in connection with recent environmental problems, but it is a big issue that the hydrogen production process includes such an environmental pollution process.

The current steam reforming process has made it possible to increase the pressure and size by making remarkable progress in desulfurization technology and reformed pipe materials as well as catalysts, and it was thought that there would be no technological innovation in recent years, but recently. Research on environmentally friendly hydrogen production methods is also being conducted in order to increase the demand for hydrogen, improve quality, improve efficiency, and take environmental measures. In addition, recently, the demand for hydrogen in relatively small-scale plants such as the semiconductor, electronics industry, and fuel cells is increasing, so in addition to the original steady-state performance required for catalysts, frequent start-ups and It is required to maintain the mechanical strength corresponding to the stop (DSS operation) and to have good load followability.

Steam reforming of hydrocarbons is carried out by:
(1) C _n H _m + nH ₂ O → nCO + (n + m / 2) H ₂
(2) CO + H ₂ O → CO ₂ + H ₂
(3) CO + 3H ₂ → CH ₄ + H ₂ O
Hydrocarbons react with water vapor and immediately convert to carbon monoxide and hydrogen, that is, syngas. Then, the water-gas shift reaction (2) continues, and a part of carbon monoxide and hydrogen is consumed in the meta-nation reaction (3).
Since the reactions of (2) and (3) have reached thermodynamic equilibrium, the composition of the final produced gas does not depend on the type of hydrocarbon as the raw material, and the reaction temperature (catalyst layer outlet temperature), pressure, etc. It is also determined by the ratio of the number of moles of water vapor to the number of carbon atoms of the raw material (water vapor / carbon ratio). Since steam reforming is a large endothermic reaction other than the water-gas shift reaction (2), it requires a high temperature of 900 ° C or higher, which is harsh for the catalyst, and this high temperature imposes major restrictions on mass transfer and heat transfer. It is characterized by being received and the conditions of use of the reformed pipe used are close to the metallurgical limit. The current large-scale hydrogen production equipment using natural gas and naphtha as raw materials is based on the ICI method and Topso method, which were constructed one after another in the 1960s. These processes, which enabled the use of heavy naphtha as a raw material, high-pressure operation of ^{30 kg / cm 2 or more, and production scale of 2 million Nm 3} / day, are used not only for the development of excellent catalysts, but also for reaction tubes. It is realized by the progress of metal materials and the progress of desulfurization technology of raw material hydrocarbons.

Based on the above background, in the present invention, bioethanol and methane are produced from unused biomass resources derived from the palm industry by renewable energy, and carbon-neutral hydrogen is produced using these. The present invention includes the following objects.
(1) Effective utilization of unused biomass resources in the palm palm industry.
(2) Manufacture of liquid fuel derived from unused biomass resources in the palm palm industry.
(3) Manufacture of gas fuel derived from unused biomass resources in the palm palm industry.
(4) Manufacture of carbon-neutral carbonized solid fuel derived from unused biomass resources in the palm palm industry.
(5) Manufacture of biomass-modified coal by mixing carbon-neutral carbonized solids derived from unused biomass resources and low-grade coal (brown coal) in the palm palm industry.
(6) Manufacture of biofuel that does not adversely affect the environment due to the use of unused biomass resources in the sustainable palm palm industry.
(7) Manufacture of high-sugar food raw materials from OPF / OPT juice derived from unused biomass resources in the palm palm industry.
(8) Reduction of carbon dioxide and conservation of the global environment by creating energy derived from unused biomass resources in the palm palm industry.
(9) Construction of an optimal system for using biomass energy to replace fossil resources (coal and petroleum).
(10) In the palm palm industry, the oil squeezing factory and the energy supply factory (company) can be separated, and the oil squeezing factory can specialize in palm oil production without the trouble of energy production, and the energy supply factory is inexpensive. Stable acquisition of biomass resources becomes possible.
(11) It enables the synthesis of DME (dimethyl ether) similar to LPG.
(12) Enables gas liquefaction (GTL), biomass liquefaction (BTL), and coal liquefaction (CTL) in one plant (however, coal liquefaction (CTL) allows the palm palm industry and coal production areas to be in the same area. Must exist).
(13) This system is an original system construction using the established ones as each technical element, and can provide highly economical energy production technology.
(14) Providing a completely new energy production technology with high mutual complementarity that is beneficial to both the country or region where the palm palm industry exists and Japan.
(15) Fusion of palm palm industry and coal industry in countries where palm palm industry and low-grade coal (mainly lignite) are produced in the same area.
(16) Realize a clean system with excellent environmental characteristics by using the manufactured biomass fuel and biomass reformed coal as they are in the existing infrastructure.

Expectations for hydrogen as a clean energy are increasing due to the recent rise in environmental problems. However, regarding the hydrogen production method, the production cost of hydrogen by decompression residual oil or partial oxidation of petroleum is considerably higher than that of steam reforming, and hydrogen by thermochemical method, photochemical method, or solar power generation and electrolysis of water. Manufacturing still has many issues to be solved, even considering the significant technological advances that are expected in the future. For this reason, it is expected that hydrogen will have to be produced by steam reforming using hydrocarbons as a raw material in the near future, so technological development aimed at further energy saving and reduction of released substances is required. ing.

In the present invention, bioethanol and methane are produced from unused biomass resources derived from the palm industry and low-grade coal by utilizing a large amount of surplus electricity and energy obtained from renewable energy, and this is comprehensively reformed into hydrogen. Provide inventions based on various processes.
In the present invention, POME, juice, and lignite are obtained as raw materials by the production method of the present invention. In addition, the energy required for production (electricity, steam, heat energy) is obtained by the production method of the present invention. Therefore, the energy cost is mainly biomass resources derived from the palm industry, and bioethanol and methane can be produced at extremely low cost, and hydrogen can be produced using these.
The optimum environment of the present invention includes Indonesia and Malaysia. Especially in Indonesia, both low-grade coal (mainly lignite) and unused biomass resources from the palm industry are the only ones in the world to exist in large quantities. It enables an independent energy company to coexist with an existing palm oil mill / palm plantation and an existing coal industry.

Renewable energy, that is, energy sources that are constantly regenerated by natural activities, supplied semi-permanently, and continuously available, are present in large quantities semi-permanently throughout the palm palm industry. If there is an environment in which coal can be obtained in the same area, it will be possible to stably produce biomass reformed coal, liquid fuel, etc., which have a low environmental impact, even for low-grade coal (mainly lignite).

The basic technique is almost established without considering the manufacturing energy cost, and this reduction in the manufacturing energy cost can be solved in the process of the present invention. In addition, it is a process that utilizes unused biomass resources derived from the palm industry, and carbon neutrality can be achieved, and electric power, steam, thermal energy, bioethanol, hydrogen, biomass semi-carbonized pellets, etc. can be produced.

The total amount of non-product biomass energy generated from a standard balm oil mill and farm is about 7 MW, and the energy used in the balm oil mill can be about 1 MW, or 6 MW, as input to the new energy mill. Furthermore, if you obtain EFB, PKS, OPT, and OPF excluding POME from the balm oil squeezing factory (about 20) and palm palm plantation (about 20 factories) within 50 km of the neighborhood, about 4 MW x 20 times = 80 MW. It will be the energy available to the energy company.

The present invention is used in two countries, Malaysia and Indonesia, which account for about 85% of the world palm oil industry.
(A) Existence of inexpensive and stable unused biomass resources,
(B) Existence of biomass fuel, which is cheap, stable and renewable energy,
(C) Existence of established existing technology (including stable technology with energy cost issues) (d) A large amount of land can be secured and can be used at a low price.
(E) It is easy to secure water in areas with constant temperature and heavy rainfall.
(F) Existence of industrial utilities established in the existing palm industry, such as transportation roads and port facilities,
(G) Existence of abundant reserves of low-grade coal (mainly lignite), especially in Indonesia,
Suitable conditions such as are satisfied.

[1] Fossil fuel reformation, hydrogenation from low-grade coal (mainly lignite) Dry and crushed low-grade coal (mainly lignite), that is, the water content has decreased and the biomass ratio has increased. Lignite has no problem as a raw material in the hydrogen production process with existing production technology, and by using unused biomass resources derived from the palm industry as a required energy source, hydrogen production is extremely economically superior. It becomes.
(1-1) Amount of hydrogen in coal:
Generally, coal is composed of an organic part and an inorganic part. Although hydrogen is contained in various fossil fuels, the hydrogen content (weight basis) of coal is about 1/3 that of petroleum and about 1/5 that of natural gas. As a rough value, if the hydrogen endowment amount of each fuel type is calculated based on the value of the endowment amount of fossil fuel, a considerable amount of hydrogen is endowed on the earth as coal.
(1-2) Hydrogen production process from coal:
Examples of the process for producing hydrogen from coal include an indirect gasification process in which coal is gasified and after refining, a hydrogen-based fuel is obtained in the same process as hydrogen production from natural gas. Even when coal is carbonized, the volatile matter in the coal can be obtained as a gas and used as a hydrogen source, but a large amount of unreacted carbon in the coal remains.
(1-3) Coal gasification process:
Gasification is an industrial method for producing hydrogen from coal. In the gasification furnace, coal is thermally decomposed (the conversion of large coal molecules into small molecules) at high temperature, and the basic reaction of carbon reacting with oxygen and water vapor to be gasified is as follows.
(A) Pyrolysis of coal → CH ₄ + C
(B) C + O ₂ → CO ₂ + 97.0 (kcal / mol)
(C) C + 1 / 2O ₂ → CO + 29.4 (kcal / mol)
(D) C + CO ₂ → 2CO + 38.2 (kcal / mol)
(E) C + H ₂ O → CO + H ₂ -31.4 (kcal / mol)
_{(F) C + 2H 2 O} → CO 2 + 2H 2 -18.2 (kcal / mol)
(G) CO + H ₂ O → CO ₂ + H ₂ + 10.0 (kcal / mol)
Generally, when the gasification temperature is low (800 to 900 ° C or less), tar content is generated more, but when gasification is performed by high temperature gasification (a thousand and several hundred ° C or more), the final content is generated. CO, H ₂ and some CH ₄ are produced as typical combustible components.
In the coal gasification furnace, _{a gas containing CO and H 2} as main components is generated by the above reaction, and the ash in the coal is removed as a solid substance. In addition, some unburned carbon is extracted from the system by the process.

[2] Hydrogenation of biomass resource POME:
For example, in Malaysia and Indonesia, more than 10 cases of obtaining methane gas from palm coconut wastewater (POME), which is wastewater from an existing palm oil mill, are in operation. However, the methane gas is gas-generated or simply incinerated, and no case of hydrogen production from POME is known. The steam reforming method, which is an already established hydrogen production method, has a high production cost at this stage, and therefore the method of locally consuming the methane gas generated in the POME generation area is an economical choice.

In most countries other than Malaysia and Indonesia, since there is no palm oil manufacturing industry, there is almost no generation of POME, and there is no environment in which other unused biomass resources can be easily obtained, so it is not possible to produce hydrogen from biomass resources. Not economical. By using methane gas from POME as a raw material and using unused biomass resources derived from the palm industry as the energy required for hydrogen reforming, hydrogen production by the steam reforming method becomes economically advantageous. The hydrogen thus obtained can be supplied to the world market. _{In addition to the advantage that hydrogen does not generate CO 2} when used, the manufacturing process is also CO ₂ free. With the addition of hydrogen, bioethanol, and methane gas-fueled transportation means, it will be completely CO _2- free hydrogen energy.

In addition, although there is an established technology for producing methanol from methane gas, there is also a problem of production cost locally, and it seems that it is not based on an actual machine. This also makes methane production economically advantageous by using unused biomass resources derived from the palm industry as the required energy.

As described above, hydrogen-based fuel synthesized from coal requires a gasification of coal and a gas refining process, so that the required energy and equipment are increased. In general, comparing gas liquefied (GTL) production from coal with an annual production of 1 million tons and gas liquefied from natural gas (GTL), both energy efficiency and economic efficiency are currently inferior to GTL from natural gas. It will be a thing.

However, considering future fluctuations in raw material prices and reduction of equipment costs due to technological innovation, GTL production from coal may be realized on an economical basis. From the viewpoint of resource quantity, coal contains hydrogen energy that is comparable to other fossil fuels. In addition, it is technically possible to convert coal into a practical fuel that can be used for fuel cells, etc. by gasifying and refining coal. However, at present, compared to hydrogen-based fuels from natural gas and the like, the number of facilities for gasification and gas refining is large, so it cannot be said that they are necessarily superior in terms of energy efficiency and economy. Therefore, hydrogen production from coal is considered to be positioned by technological development of future conversion processes and energy price trends.

The above can be summarized as follows.
[conditions]
(1) Unused biomass resources (POME, OPF, OPT, EFB, PKS) derived from the palm industry exist.
(2) There is a situation where a combined production system of the existing palm industry and high value biomass mixed fuel production is possible.
(3) POME: Unused wastewater, current valueless material, OPF / OPT: Unused biomass, current valueless, EFB: Unused biomass, current valueless, PKS: Self-consumption is about 20%, and others are sold.
(4) There is a vast site (the cost of factory land is extremely low) owned by the palm palm industry.
(5) Available logistics of the palm palm industry (no need for new development).
[means]
(1) Utilize existing technology (production of low-grade coal (brown coal) dry crushed product, hydrogen production by steam reforming method, etc.).
(2) Indonesia, which is a major country in the palm industry, is a producer of low-grade coal, and because it meets both conditions, a combined production system is possible.
(3) Technology for using existing palm oil squeezing factories, new high-value-added biomass fuel manufacturing factories, and nearby low-grade coal (brown coal) production areas, and manufacturing required energy from unused palm-derived biomass resources It will be an economical combined production technology for hydrogen production that will be possible only by combining the elements.

[3] Hydrogenation of OPF and OPT sap, which are unused biomass resources derived from the palm industry:
Since the juice obtained by squeezing old palm trees (OPT) and palm branches and leaves (OPF) contains a large amount of sugar, it is possible to produce bioethanol and methane gas by fermentation, such as JIRCAS (Japan International Research Center for Agriculture, Forestry and Fisheries). Proven in. In Malaysia and Indonesia, which are the major countries of the palm palm industry in the world, the use of old palm trees (OPT) (excluding the use of exodermis) has not made much progress due to the stability of arrival and the uneconomical production cost. Palm foliage (OPT) has not been implemented on a business scale, and in countries other than Malaysia and Indonesia, the palm palm industry has not been scaled up, and energy conversion by using biomass resources, especially hydrogen production, is economical. It wasn't the target.

Using methane gas obtained by methane fermentation from the juice of old palm trees (OPT) and palm branches and leaves (OPF) as a raw material, the energy required for gas reforming is hydrogen by using unused biomass resources derived from the palm industry. Hydrogen production by the steam reforming method, which is a general method of production, is economically advantageous. The produced hydrogen can be supplied to the world market. In addition, although there is an existing technology that has established the production of methanol rather than methane gas, there is a problem of manufacturing cost, and it is presumed that there is a big economic problem on an actual machine basis. In the present invention, methanol production becomes economically advantageous by using unused biomass resources derived from the palm industry as the required energy.
_{In addition to the advantage that hydrogen does not generate CO 2} when used, the manufacturing process is also CO ₂ free. With the addition of hydrogen, bioethanol, and methane gas-fueled transportation means, it will be completely CO _2- free hydrogen energy.

The above can be summarized as follows.
[conditions]
(1) Unused biomass resources (POME, OPF, OPT, EFB, PKS) derived from the palm industry exist.
(2) There is a situation where a combined production system with the existing palm industry is possible.
(3) POME: Unused wastewater, current valueless material, OPT / OPF: Unused biomass, current valueless, EFB: Unused biomass, current valueless, PKS: Self-consumption is about 20%, and others are sold.
(4) There is a vast site (the cost of factory land is extremely low) owned by the palm industry.
(5) There are available logistics (no need for new development) of the palm industry.
[means]
(1) Existing technologies (bioethanol production from OPT / OPF juice, hydrogen production by steam reforming, etc.) can be used.
(2) It will be possible with a complex production technology for hydrogen production that has an existing palm oil squeezing plant and uses unused biomass resources and renewable energy derived from the palm industry.

The following can be realized by the method for producing hydrogen using unused biomass resources derived from the palm industry of the present invention.
(1) The generation of methane gas from POME can be effectively used to suppress the generation of greenhouse gases.
(2) Hydrogen production using methane gas obtained from POME reduces energy costs, transportation costs, equipment construction costs, etc., enabling hydrogen production at a low cost that has never been possible before. ..
(3) By effectively utilizing methane gas, etc. released into the atmosphere due to the decay of unused biomass resources derived from the palm industry, the generation of greenhouse gases is suppressed.
_{(4) A CO 2} reduction effect is obtained by hydrogen production using unused biomass resources derived from the palm industry and renewable energy.
(5) Hydrogen production from OPT / OPF juice is also replaced by the _{above-mentioned CO 2 reduction effect.}
(6) Expand the applications of low-grade coal (mainly lignite).
(7) Since low-grade coal (mainly lignite), which is difficult to export as it is, is converted into hydrogen, energy transfer different from the current state becomes possible. The same is true for bioethanol.
(8) The cost of producing hydrogen from low-grade coal (mainly lignite) is greatly reduced by the framework of the present invention.
(9) Since all the energy for producing hydrogen from low-grade coal (mainly brown coal) is covered by renewable energy derived from biomass, CO ₂ emissions can be achieved by using fossil fuel energy to produce hydrogen by the steam reforming method. It is greatly reduced in comparison.
(10) A huge amount of new renewable energy can be produced in factories in an extremely stable and inexpensive manner.
(11) Unused biomass resources derived from the palm industry have little seasonal fluctuation, are generated stably, and there is no major disturbance, so that a stable energy supply will be provided in the future.
(12) The energy supply companies can be separated, the efficient operation of the existing palm palm industry is promoted, the environmental load (air and water quality) of the palm palm industry can be reduced, and the cost can be reduced.
(13) It will contribute to securing energy in the area where the palm palm industry is located, and will be able to expand local employment, increase profits, and make effective use of low-grade coal (brown coal) by converting energy.

Hereinafter, a method for producing hydrogen using a biomass resource according to an embodiment of the present invention for solving the above-mentioned background and problems will be described with reference to the drawings. Each of the embodiments shown below will be specifically described in order to better understand the gist of the invention, and is not limited to the present invention unless otherwise specified.

First, with reference to FIG. 1, the outline of the method for producing hydrogen using the biomass resource of the present invention will be described.
FIG. 1 is a block diagram showing an outline of a method for producing hydrogen using a biomass resource according to an embodiment of the present invention.
The method 10 for producing hydrogen using the biomass resource of the present invention includes a palm oil production process 13 for obtaining palm oil from a palm coconut tree, a harvesting and sorting process 11 for obtaining a recycled raw material from a palm coconut tree, and a half biomass from the recycled raw material. Methane is produced using the semi-carbonized process 12 and the emissions (for example, separated water) produced in the palm oil production process 13 to produce carbides and bioethanol, and steam reformed together with the bioethanol obtained in the semi-carbonized process 12. It has a hydrogen production process 14 for obtaining hydrogen by means of.

In the harvesting and sorting process 11, fresh palm coconut bunches (FFBs) cultivated on palm plantations are harvested. In addition, palm branches and leaves (OPF: recycled raw material) are obtained when harvesting fresh fruit bunches (FFB) of palm palm.

In the palm oil production process 13, palm oil and palm kernel oil are squeezed from the harvested fresh fruit bunches (FFB). In the palm oil production process 13, the separated water, which is the waste produced by the oil-water separation performed when producing palm oil, the empty fruit bunch (discharge) after the fruit is removed from the fresh fruit bunch (FFB), and the palm oil. Palm coconut shells (emissions) and palm fibers (emissions) that are discharged after oil extraction are discharged.

In the semi-carbonization process 12, fresh fruit bunches (FFB) are squeezed from palm branches and leaves (OPF), which are recycled raw materials obtained at the time of harvesting, and then the squeezed residue is semi-carbonized to obtain biomass semi-carbonized products. Further, in this semi-carbonization process 12, the juice produced by the juice of palm branches and leaves (OPF) is fermented to produce bioethanol, which is a by-product.

In the hydrogen production process 14, methane is produced by fermentation using the separated water which is the discharge of the palm oil production process 13. Then, using this methane and bioethanol, which is a by-product of the semi-carbonization process 12, hydrogen gas is generated by steam reforming.

In the hydrogen production process 14, renewable energy such as heat energy and electric power is generated by combustion or the like using empty fruit bunches, palm coconut shells, palm fibers, etc., which are emissions of the palm oil production process 13. Then, steam reforming is performed using this renewable energy as an operating energy source.

According to the method 10 for producing hydrogen using biomass resources of the present invention, a palm oil production process is used as an operating energy source for a steam reforming process that requires a large amount of energy to create a high temperature environment such as 700 ° C. to 1000 ° C. Renewable energy using 13 emissions is used. As a result, the wastes of the palm oil production process 13, such as empty fruit bunches, palm coconut shells, and palm fibers, can be effectively used, and steam reforming can be performed without procuring electric power or thermal energy from the outside. By the method, hydrogen gas can be produced at low cost. In addition, wastes such as empty fruit bunches, palm coconut shells, and palm fibers discharged in the palm oil production process 13 can be treated at no cost, and the wastes can be reduced to protect the environment. Becomes possible.

FIG. 2 is a schematic explanatory view showing in more detail a method for producing hydrogen using the biomass resource shown in FIG. Further, FIG. 3 is a flowchart showing a stepwise method for producing the biomass reformed coal according to the embodiment of the present invention. In FIG. 3, the region surrounded by the dotted line indicates that the energy indicated by the arrow extending toward the region and each substance are supplied to an arbitrary process included in the region. Further, in FIG. 3, the region surrounded by the alternate long and short dash line indicates that a certain process is composed of a plurality of processes (lower processes).
Further, in the following description, the term lignite refers to low-grade coal having a low degree of coalification (for example, carbon content of 70 wt% or less), and subbituminous coal, bituminous coal, and anthracite coal having a higher degree of coalification. Includes all excluded coal.

The hydrogen production method 10 using renewable energy using unused biomass resources derived from the palm industry and brown charcoal (low quality coal) as raw materials is roughly divided into palm palm harvesting, sorting process 11, and semi-carboning process. 12, a palm oil production process 13, a biomass reformed coal production process 14, and a hydrogen production process 17 including a steam reformed hydrogen production process 15 and a water electrolytic hydrogen production process 16. It is preferable that the facilities that carry out each of these processes are physically close to each other or integrated with each other in terms of transportation efficiency. Further, the biomass reformed coal production process 14 is not an essential configuration, but is a step that can be preferably performed when brown coal, which is a low-grade coal, is available in the vicinity of the palm palm plantation.

Palm palm has a hot and humid climate with a range of 17 degrees north latitude to 20 degrees south latitude centered on the equator, annual rainfall of 1500 to 2000 mm, minimum temperature of 22 to 24 ° C, maximum temperature of 29 to 30 ° C, and sunshine hours of 5 hours / day or more. Is a favorable environment for cultivation, and Southeast Asia, Africa, and Central and South America are considered to be suitable for cultivation.

Oil palms cultivated in plantations are sprouting from seeds, grown in pots for about one to one and a half years, and then planted on the leveled land at a density of about 140 to 150 trees / ha. Three years after planting, the first inflorescence appears at the base of the leaf, and eventually all the inflorescences follow the root of the leaf. There are male and female inflorescences, and the male flowers are yellow and small, and pollen is produced 3 to 4 days after they appear. Female flowers are also yellow flowers, and 10 to 12 inflorescences form one inflorescence, and these inflorescences gather to form an inflorescence. Since pollen does not fly very long, pollination is carried out through insects.

Fruits mature about 150 days after pollination. Harvesting begins three to four and a half years after germination, with trees eight to fifteen years being best harvested. About 11 fresh fruit bunches (FFB) can be harvested annually from one palm palm, and two palm branches and leaves (OPF: recycled raw material) are cut during this harvest. After about 18 years, the yield begins to decrease, so it is usually cut down and replanted in about 20 to 25 years.

FIG. 4 is a schematic view showing each constituent part of the palm palm.
As shown in FIG. 4, the palm palm 1 is generated at the root portion of the trunk 2 rising from the ground, the palm branches and leaves (OPF: recycled raw material) 3 branching and extending from the trunk 2, and the palm branches and leaves (OPF) 3. It has a fruit bunch (fresh fruit bunch) 5 that bears a large number of fruits 4.

FIG. 5 is a schematic view showing palm branches and leaves (OPF) of palm palm.
The palm branch leaf (OPF) 3 is composed of a leaf portion (Rachis) 6 on which a palm leaf grows and a petiole 7 forming a petiole 5 side of the leaf portion 6.

FIG. 6 is a schematic view showing a cross section of a palm palm fruit.
The fruit 4 is composed of an outer pericarp 4A, a flesh (medium pericarp) 4B containing palm oil, and a palm coconut core 4C wrapped in the inner pericarp and containing palm kernel oil.

In the harvesting and sorting process (harvesting step S1) 11, the fresh fruit bunches (FFB) of palm palms cultivated in the palm plantation are harvested. In addition, when harvesting the fresh fruit bunch (FFB) of palm palm, it is necessary to cut down the palm branches and leaves (OPF) growing around the fresh fruit bunch (FFB). When harvesting one fresh fruit bunch (FFB), two palm branches and leaves (OPF) will be cut down.

The palm branches and leaves (OPF) obtained in the harvesting and sorting process 11 are further cut into leaf parts (Rachis) on which palm leaves grow and petioles (Petioles) forming a fresh fruit cluster (FFB) side from the leaf parts. Then, in the following semi-carbonization process 12, petioles are used as palm branches and leaves (OPF). Of course, it can also be used in the semi-carbonization process 12 including the leaves. In the palm branch leaf (OPF) 3, the weight ratio of the petiole 7 to the leaf portion 6 is about 50:50. The petiole 7 of the palm branch leaf (OPF) 3 is characterized in that the starch content is particularly high from the root (base) connected to the trunk 2 to the central portion.

On the other hand, the carved leaf part (Rachis) 6 is laid around the palm palm under cultivation of the palm palm plantation. By placing a leaf part (Rachis) with such a large number of leaves around the palm palm, a habitat for snakes that prey on wild rats aiming at the palm palm fruit cluster is secured, and the palm palm is prevented from being damaged by rats. To do.

By the above harvesting and sorting process (harvesting step S1) 11, the petioles 7 of fresh fruit bunches (FFB) and palm branches and leaves (OPF) are obtained. In addition, for example, palm palm 1 that has been used for more than 20 years is also cut down and collected as old palm trees (OPT) and remaining palm branches and leaves (OPF).

The trunk of old palm trees (OPT) contains a large amount of sap, and the content of the sap tends to be higher toward the central part, but the average is about 65% to 85%. This old palm tree (OPT) is an excellent sugar solution that is very high in glucose, fructose, and sucrose. Although there are some differences depending on the age of old palm trees (OPT), the total sugar content immediately after logging is about 7 to 10%. Looking at the same trunk, the distribution of sugar content above and below it is about 20% lower at the bottom, but about the same from the middle to the top.

It is also known that old palm trees (OPT) have a change that can be said to be a ripening phenomenon, in which the sugar content is greatly increased by storing the trees for a certain period of time after logging. For example, it is known that the sap content immediately after logging is 65% to 85% and hardly changes during the storage period, while the sugar content rises up to nearly 15%. Considering that the sugar content of sugar cane juice is about 16% as an example, old palm trees (OPT: recycled material) can become a raw material having a sugar content equivalent to sugar cane after an appropriate aging period. There is sex. For this reason, it is also preferable to store old palm trees (OPT) after logging for a certain period of time to increase the sugar content.

The fresh fruit bunches (FFB) that have undergone the harvesting and sorting process (harvesting step S1) 11 are sent to the palm oil production process 13, and the palm branches and leaves (OPF: recycled raw material) are sent to the semi-carbonized process 12.

First, the semi-carbonization process 12 will be described. In the semi-carbonization process 12, the petioles 7 of palm branches and leaves (OPF) are washed. Use water for cleaning. It is preferable that the washing wastewater used for washing the petiole 7 is recycled as reclaimed water by performing a step such as precipitation.

Next, the washed petioles 7 are dehydrated or dried. The petiole 7 is preferably dried in the sun, for example. It can also be dried using a dryer with warm air or the like. It can also be dehydrated using a dehydrator.

The petiole 7 of the palm branch leaf (OPF) roughly cut to about 0.5 to 1 m for handling in the harvesting step S1 is sent as it is to the juice squeezing step S3 described later, but is harvested and sorted together with the petiole 7. Old palm trees (OPT: recycled raw material) recovered in the process (harvesting step S1) 11 can also be used by crushing (first crushing step S2). By using such an old palm tree (OPT) together with the petiole 7, the old palm tree (OPT), which was difficult to utilize due to insufficient strength as a tree, can be effectively utilized.

Next, juice is squeezed from the old palm tree (OPT) and the leaf stalk 7 crushed in the first crushing step S2, and the obtained juice and the crushed product of the first solid residue (the leaf stalk 7 and the old palm tree (OPT) (for example). The sap is squeezed from a lump of about 50 mm or less) and is separated (juice step S3). When squeezing crushed petioles 7 or old palm trees (OPT), for example, a roller press type squeezing machine used for squeezing sugar cane can be used.

The juice juice and the first solid residue can be separated by a separation method such as centrifugation or filtration. The separated juice liquor forms, for example, a yellowish turbid liquid and contains a large amount of sugar components. Bioethanol, which is a biofuel, and food raw materials are produced using such juice (bioethanol production step S4). Further, in the bioethanol production step S4, a food raw material can be produced using the sugar component of the juice squeezed liquid.

The bioethanol production step S4 includes, for example, a concentration step S4A, a fermentation step S4B, and a purification step S4C. In the concentration step S4A, the juice is concentrated to the extent that it can be efficiently fermented. The concentration step S4A can be performed, for example, by centrifuging the juice or reducing the water content by heating.

In the fermentation step S4B, the sugar component contained in the juice is converted to methane gas or bioethanol by fermentation. For example, by alcoholic fermentation (Ethanol Fermentation), sugar components (glucose, fructose, sucrose) are decomposed to produce ethanol (bioethanol) and carbon dioxide.

In the purification step S4C, bioethanol and sugar components are purified to remove impurities to obtain bioethanol with higher purity. In addition, the sugar component produced by fermentation can be used as a food raw material. The bioethanol obtained in such a bioethanol production step S4 is used as one of the hydrogen generation raw materials in the steam reforming hydrogen generation process 15 described later.

The amount of squeezed liquid produced in the squeezing step S3, which is the previous process, is relatively large, and if it is discharged as it is, there is a concern about water pollution. By doing so, it is possible to make effective use of the squeezed liquid and prevent water pollution caused by the squeezed liquid. At present, old palm trees (OPT) rot while being crushed or cut down on farmland, and two palm branches and leaves (OPF) are also cut off at the time of FFB harvest and left on the spot, so they rot and become a source of environmental pollution. It has become.

On the other hand, in the squeezed cake which is the first solid residue obtained in the above-mentioned juice squeezing step S3, a crushed palm foliage is formed by crushing (second crushing step S5). The squeezed cake of the first solid residue may be crushed by, for example, a crusher provided with a rotary blade. The crushed palm foliage obtained thereby is, for example, in the present embodiment, a crushed product having a size of, for example, about 50 mm or less. It is also selected by the juice squeezing method to provide a crushing process before the juice squeezing process.

In the second crushing step S5, the crushed empty fruit bunch (EFB) after the fruit was degreased in the palm oil production process 13 described later, and the palm coconut shell (PKS) after the fruit was squeezed were transferred to palm branches and leaves. Can be added to crushed material. In addition, in the following description, it is described as a palm branch and leaf powder including those to which such an empty fruit bunch powder and a palm coconut shell powder are added.

One of the advantages of semi-carbonization by the drying step S6A and the semi-carbonization step S6B, which will be described later, is the reduction of crushing power. Since the palm branches and leaves (OPF) and old palm trees (OPT) are fragile, the power load is small for some crushing before the semi-carbonization process S6B, but the power load for crushing the empty fruit bunch (EFB) is before the semi-carbonization process S6B. Crushing power load is large. Therefore, regarding the empty fruit bunch (EFB), after crushing to, for example, about 50 mm to 150 mm in the second crushing step S5 before the semi-carbonization step S6B, the drying step S6A and the semi-carbonization step S6B for adjusting the water content are performed. By pulverizing to about 15 mm or less, the power load is reduced, which is economically preferable.

Next, using the crushed palm foliage obtained in the second crushing step S5, a biomass semi-carbide which is a raw material for biomass reformed coal described later and a fuel pellet using the same are produced (fuel pellet manufacturing step). S6). The fuel pellet manufacturing step S6 includes a drying step S6A, a semi-carbonization step S6B, a pulverization step S6C, and a compression molding step S6D. In the semi-carbonization step S6B, the palm foliage crushed product obtained in the second crushing step S5 is semi-carbonized by a semi-carbonization furnace. By semi-carbonizing the dried product after crushing the palm branches and leaves in an atmosphere of, for example, 300 ° C. or lower and less than 10% oxygen, the calorific value can be improved by 20 to 30% and the water resistance can be improved.

The products in the second crushing step S5 have a water content of about 40% in the case of palm branches and leaves (OPF) and old palm trees (OPT), and about 50% in the case of empty fruit bunch (EFB). Therefore, it depends on the equipment whether the drying step S6A to the semi-carbonizing step S6B is performed once or these steps are performed in two steps, but the water content is usually about 10 to 13% after the drying step S6A. In the subsequent semi-carbonization step S6B, the water content is 12% or less, preferably around 5% (then, 8 to 10% due to moisture absorption).

The drying equipment for adjusting the water content includes, for example, a belt dryer or a rotary heat treatment furnace. The semi-carbonization process, which is the next step, keeping the water content of the input material constant is important for the semi-carbonization treatment, which is the next step, and it is required that the outlet moisture content be stable at about 13% or less. Be done.

The semi-carbonization treatment apparatus for performing the semi-carbonization treatment may be, for example, a rotary heat treatment furnace. Using such a rotary heat treatment furnace, the palm foliage powder is heated to, for example, about 200 ° C. to 350 ° C. and held for 5 to 90 minutes to bring the water content to about 0% to 12%.

The operating energy source required for the operation of the heat treatment furnace used for the semi-carbonization treatment (trefide) is obtained by the energy generation step S16 described later using palm coconut shell (PKS: waste) and palm fiber (Fiber: waste). The generated electric power, steam and thermal energy can be used.

By the semi-carbonization step S6B as described above, a semi-carbonized biomass semi-carbonized product obtained by semi-carbonization treatment (trefide) from the first solid residue is obtained. This biomass semi-carbide is used as a raw material for producing biomass reformed coal, which will be described later. The biomass semi-carbide can also be used as a raw material for the fuel pellets described below.

When biomass semi-carbide is used for the production of fuel pellets, palm-derived lignin is added to the biomass semi-carbide, which is a semi-carbonized palm branch and leaf crushed product, and then compression molding is performed to pelletize (compression molding). Step S6D). In the compression molding step S6D, for example, a die extrusion type pellet molding apparatus can be used. Also in such a compression molding step S6D, for example, it was obtained by an energy generation step S16 described later using an empty fruit bunch (EFB), a palm coconut shell (PKS), a palm fiber (Fiber), etc. as a driving source of the pellet molding apparatus. Renewable energies such as electric power, steam and thermal energy can be used.

In the compression molding step S6D, the amount of lignin in the input material is related to the degree of molding of the pellets, but when adjusting the amount of lignin, lignin derived from palm can be used. Further, the material size before pellet molding needs to be adjusted by crushing depending on the pellet diameter to be molded. Further, in the above-described embodiment, in the fuel pellet manufacturing step S6, the compression molding step S6D is performed after the semi-carbonization step S6B, but the semi-carbonization step S6B may be performed after the compression molding step S6D. it can. In this case, the dimensions of the raw material input to the compression molding step S6D are determined by the pellet diameter to be molded.

Normally, in the case of wood, the energy required for pretreatment crushing of the pellet molding machine input is embrittlement due to semi-carbonization, so the crushing energy decreases as the degree of semi-carbonization progresses. Therefore, it is preferable to perform the compression molding step S6D after the semi-carbonization step S6B.

On the other hand, palm branches and leaves (OPF) or old palm trees (OPT) have a fragile tissue, so that the energy required for crushing is small. Therefore, it is also preferable to perform the compression molding step S6D and then the semi-carbonization step S6B. Further, since the empty fruit bunch (EFB) structure is non-fragile, it is preferable that the semi-carbonization step S6B is followed by the pulverization step S6C and the compression molding step S6D.

Through the above steps, fuel pellets, which are solid biomass fuels, can be obtained.
In the present embodiment, the compression molding step S6D is carried out after the semi-carbonization step S6B is carried out, but such steps can also be carried out in the reverse order. That is, the crushed palm foliage obtained in the second crushing step S5 is pelletized by the compression molding step S6D, and then the pellets are semi-carbonized by the semi-carbonization step S6B using a heat treatment furnace or the like to obtain a biomass semi-carbide. Then, using this biomass semi-carbide, pellets for fuel can also be produced.

Fuel pellets are made by pelletizing semi-carbonized palm foliage powder. The fuel pellet has, for example, a substantially cylindrical shape, and has a diameter of 4 mm to 20 mm and a length of 5 mm to 100 mm. Further, the bulk specific gravity is set to be in the range of 0.65 or more and 0.85 or less.

Biomass semi-carbide that has undergone the semi-carbonization step S6B can be used not only in pellet shape but also in bio-coke briquettes, which are alternative fuels for coal coke, for example, products with a diameter of 50 to 150 mm and a length within the range of (diameter) x 1 to 5. It can be molded.

Although the water content and volatile components of the fuel pellets are reduced by dehydration treatment and semi-carbonization treatment, the water content of the fuel pellets is adjusted within the range of 12% or less, and the calorific value is 20 kJ / kg or more and 24 kJ. It is said to be within the range of / kg or less.

Further, in the fuel pellet 20, the Hardgrove Grindability Index (HGI) defined by JIS M 8801 is in the range of 22 or more and 50 or less. As a reference example, the lower limit of operation for a pulverized coal boiler is HGI = 40 or more.
In addition, the fuel pellet has a hydrophobic surface due to semi-carbonization treatment, and has improved water resistance. Even if it is immersed in water, it does not easily collapse and its shape is maintained. ..

On the other hand, the squeezed juices (OPT / OPF-Juice) derived from palm palm produced in the above-mentioned juice squeezing step S3 and fuel pellet manufacturing step S6 are aggregated and used in the bioethanol production step S4 to concentrate and ferment. , Purification can be performed.

By collecting the squeezed liquid containing the sugar component derived from coconut produced in each step constituting the semi-carbonization process 12 and using it in the bioethanol production step S4, it was discarded in the farm, spoiled, and released methane gas. Palm branches and leaves (OPF) and old palm trees (OPT) can be effectively used as biomass resources.

In the energy generation step S16, the empty fruit bunch (EFB: discharge) and palm fiber (Fiber: discharge) generated in the fruit removal step S11, and the palm coconut shell separated in the coconut core separation step S14 (EFB: discharge). PKS: Emissions) are burned to generate heat energy, and this heat energy is used to heat water to generate steam (high temperature steam), electric power, and the like. The heat energy and steam (high temperature steam) obtained in the energy generation step S16 are used in the steam reforming hydrogen generation process 15 described later, and the electric power is used in the steam reforming hydrogen generation process 15 and the water electrolysis hydrogen generation process 16. be able to.

Further, the heat energy and electric power obtained in the energy generation step S16 are used in each step (brown coal drying step S21, brown charcoal crushing step S22, mixing step S23, compression molding step S24) which is a biomass reformed coal manufacturing process 14 described later. It can also be used as an operating energy source.

Next, the palm oil production process 13 will be described.
In the palm oil production process 13, after washing the fresh fruit bunches (FFB), the fresh fruit bunches (FFB) are steamed and separated into fruits and empty fruit bunches (EFB) (fruit removal step S11). Since palm palm contains a lipase enzyme that decomposes oil in the fruit, this lipase enzyme is activated from the moment of harvesting. Therefore, it is necessary to apply heat within 24 hours after harvesting the fresh fruit bunch (FFB) to inactivate the lipase enzyme.

The purpose of steaming these fresh fruit bunches (FFBs) is to inactivate (inactivate) the enzymes that break down oil. For such inactivation, for example, in the rotary steaming process, the operation of swinging the pressure a few times with the maximum temperature of 140 ° C. (pressure + 2 atm) peaking is performed for 75 to 90 minutes. Further, by steaming, the fruits are easily separated from the fruit bunches, and the fruits are softened to facilitate oil extraction in the palm oil production process 13. To separate the fruit from the fruit cluster, for example, the fruit cluster is beaten using a fruit remover or the like to separate the fruit from the stem and fruit of the fruit cluster.
After that, in order to efficiently squeeze the separated fruits, the fruits are stirred for about 30 minutes while heating at 95 ° C. to 100 ° C. with steam to form a slurry (digestion).

In such a fruit removal step S11, the fresh fruit bunch (FFB) can be steamed using the steam obtained in the above-mentioned energy generation step S16. The fruit removal step S11 uses the largest amount of steam in the palm oil production process 13.

Further, the empty fruit bunch (EFB) after fruit removal generated in this fruit removal step S11 is introduced into the second crushing step S5 in the semi-carbonization process 12 described above after dehydration to some extent, and is one of the palm branches and leaf powder. By using it as a raw material for manufacturing fuel pellets, it is possible to reduce wood waste and make effective use of it. Further, the empty fruit bunch (EFB) after fruit removal can also be crushed by using the first crushing step S2 of the old palm tree.

Next, the fruit slurried in the fruit removing step S11 is squeezed (first oil squeezing step S12). For example, in the first oil squeezing step S12, a screw type oil squeezing machine is used to separate the crude palm oil and the second solid residue which is a fibrous material containing palm coconut nuclei by pressure.

Next, the crude palm oil obtained in the first oil extraction step S12 is hydrated, heated to, for example, about 85 ° C. and allowed to stand, and then oil-water separation is performed according to the difference in specific gravity to perform palm oil and second palm palm. Wastewater (POME) is obtained (oil-water separation step S13). It is also possible to quickly separate oil and water by further removing fibers, water and the like with a centrifuge after water addition.

The separated water (POME: discharge) separated in the oil-water separation step S13 cannot completely separate and remove the coconut-derived fats and oils dissolved in the aqueous layer even by the oil-water separation, and a certain amount of coconut-derived fats and oils are removed. Includes. This separated water (POME) is used as a raw material for the methane production step (fermentation step) S17 described later.

In the methane production step (fermentation step) S17, the oil and sugar components remaining in the separated water (POME: discharge) separated in the oil-water separation step S13 are fermented by, for example, methane bacteria to produce methane. The methane thus obtained in the methane production step (fermentation step) S17 is used as one of the hydrogen producing raw materials in the steam reforming hydrogen producing process 15 described later.

As described above, by producing methane in the methane production step (fermentation step) S17 using the separated water (POME) containing fats and oils derived from palm produced in the oil-water separation step S13 constituting the palm oil production process 13. In addition to preventing water pollution due to the discharge of palm palm-derived wastewater (POME) to the outside, which has been a problem in the past, it is possible to effectively reuse such wastewater (POME).

The methane produced by the methane production process (fermentation process) S17 from the separated water (POME), which is an unused biomass resource, can be used for biomass power generation and combustion energy by methane gas in addition to the steam reforming hydrogen production process 15 described later. It can be obtained and used as self-consumed energy or sold as a valuable resource.

By recovering methane, which is a huge greenhouse gas generated from the separated water (POME) treatment plant lagoon containing fats and oils derived from coconuts, which was generated in the first oil extraction step S12, in addition to self-consumed energy, It is possible to prevent global warming by using methane gas and water pollution by POME-treated wastewater. Furthermore, it is possible to sustainably operate palm coconut farms that are suitable for environmental conservation of air and water quality, such as purification of river effluent and adsorption of efmic acid and pigments of effluent by unused biomass solid carbides.

On the other hand, the second solid residue contains a palm coconut kernel, and after the second solid residue is dried and crushed, the palm coconut kernel and the palm coconut shell (PKS) are separated (palm nucleus separation step S14). Such separation can be done, for example, by air flow. Then, the separated palm coconut kernel is squeezed to obtain palm kernel oil (second oil squeezing step S15).

On the other hand, a part of the palm coconut shell (PKS) separated in the coconut nucleus separation step S14 is sold as a valuable fuel having marketability as it is, but there are cases where the water content is not constant and it dries. However, there are problems such as subsequent moisture absorption and an increase in drying cost. In the present embodiment, the palm coconut shell (PKS) may be added to the pellet manufacturing process S6 for fuel derived from palm branches and leaves (OPF) or manufactured independently, and the manufacturing cost is lower than that of the current dried product. Moreover, it can be made into a biomass semi-carbide which is a semi-carbide derived from palm coconut shell (PKS) which is very hydrophobic and very close to coal.

Further, the steam obtained in the energy generation step S16 can be used as saturated steam for steaming the fresh fruit bunch (FFB) in the fruit removal step S11. Further, the electric power is used as a driving force of the heat treatment furnace in the semi-carbonization step S6B in the fuel pellet manufacturing step S6, the operating energy source of the pellet molding apparatus in the compression molding step S6D, and the biomass reformed coal manufacturing process described later. It can be used as an operating energy source for each step (brown coal drying step S21, brown charcoal crushing step S22, mixing step S23, compression molding step S24).

Further, another part of the palm coconut shell (PKS) separated in the coconut kernel separation step S14 was introduced into the second crushing step S5 in the semi-carbonization process 12 described above, and was half as a part of the crushed palm foliage. The biomass is semi-carbonized through the carbonization step S6B and sent to the mixing step S23, which is the biomass reformed coal production process 14 described later, and can be used for producing the biomass reformed coal. As a result, it is possible to reduce wood waste and make effective use of it. These are also the same for palm fiber (Fiber) and empty fruit bunch (EFB).

Next, the biomass reformed coal production process 14 will be described.
In the biomass reformed coal production process 14, lignite is used as a raw material. As explained in the above-mentioned technical background, such lignite is a low-grade coal with a low degree of coalification (for example, a carbon content of 70 wt% or less), which is often produced in Indonesia and the like. In the following biomass reformed coal production process 14, it is preferable to use brown coal obtained from a coal mine existing in the vicinity of the palm palm industry in which the above-mentioned semi-carbonization process 12 and palm oil production process 13 are carried out. As a result, it is possible to suppress the transportation cost of lignite and spontaneous combustion due to ignitable functional groups associated with the drying of lignite.
Low-grade coal reforming technology is already in the stage of practical use, with measures to improve calorific value and spontaneous ignition, centered on the development of dehydration reforming technology, and commercialization plans are underway. , Many technologies have not been commercialized for economic reasons.

Lignite is usually dark brown to brownish. It has more dark coal than the higher grade bituminous coal and is rich in water, humic acid and oxygen. The proportion of ash (minerals) varies depending on the coal-mining region. It is characterized by the fact that water accounts for more than half of the weight (66% in the case of a large amount). This is because the pore volume of lignite is large (there are many gaps), so that water easily penetrates. First, the lignite is dried by efficiently and safely evaporating such water (lignite drying step S21). When the mined lignite is in the form of a large lump, it is preferable to crush the lignite in advance until it reaches a predetermined size by the lignite crushing step.

In the lignite drying step S21, the amount of water in the lignite is reduced while preventing the flammable functional groups contained in the lignite from spontaneously igniting due to the evaporation of water. Specifically, an indirect heating method is used to dry the lignite. Saturated steam is used as the heat source. In order to reduce the amount of heat consumed in the lignite drying step S21, it is preferable that the waste heat is further recovered by the heat recovery unit in the condensate from the dryer and returned to the steam generation unit. For example, air or nitrogen gas is sent to the dryer to adjust the rate of water evaporation. The outlet gas of the dryer contains steam, air (or nitrogen), and lignite fines, and a bag filter is used to remove the lignite fines before they are released into the atmosphere.

Next, the lignite dried in the lignite drying step S21 is crushed to produce fine powdered lignite of a predetermined size (lignite crushing step S22). Since the particle size distribution and water content of the powdered lignite obtained by crushing greatly affect the quality of the biomass-modified coal obtained in the subsequent process, care must be taken in controlling it. By circulating flammable gas and inert gas and controlling the oxygen concentration in the crushing atmosphere, ignition due to crushing and drying is suppressed, and safety is improved.

A part of the powdered lignite obtained in the lignite drying step S21 is used for the production of biomass reformed coal, and the remaining part is used for hydrogen production by the steam reformed hydrogen production process 15 described later.

Next, the powdered lignite obtained through the lignite crushing step S22 and the biomass semi-carbide obtained from palm branches and leaves (OPF) and old palm trees (OPT) in the semi-carbonization step S6B of the semi-carbonization process 12 are mixed. To obtain a mixture (mixing step S23).

In this mixing step S23, the powdered brown charcoal and the crushed biomass semi-carbide are mixed at a predetermined mixing ratio by using a mixing device (mixer) for powder. In the present embodiment, a mixture of powdered lignite and biomass semi-carbide is mixed at a weight ratio of 50:50 is formed.

Next, the mixture of the powdered lignite obtained in the mixing step S23 and the biomass semi-carbide is compression-molded to obtain a briquette-shaped biomass-modified coal (compression molding step S24). In the compression molding step S24, for example, a briquette machine is used for compression molding. By optimally setting the shape and size of the briquette, the roll rotation speed, and the roll supporting pressure, it is possible to produce high-strength, high-density briquette-shaped biomass reformed charcoal without using a binder, and at the same time reduce power consumption. it can.

In these series of biomass reformed charcoal production processes 14, the first operating energy generated from the juice squeezed liquid obtained in the juice squeezing step S3, the empty fruit bunch (EFB), the palm coconut shell (PKS), and the palm fiber (Fiber). The second operating energy obtained from) and the third operating energy obtained from the separated water (POME) are used in each step (brown coal drying step S21, brown charcoal crushing step S22, mixing step S23, compression molding step S24). It can be used as an operating energy source for. As a result, biomass reformed coal can be produced at low cost without adding new energy (electric power, steam, etc.) from the outside.

Next, the steam reformed hydrogen generation process 15 will be described.
In the steam reforming hydrogen generation process 15, hydrocarbon gas is generated from the powdered brown coal obtained through the first gasification step S31 for gasifying the bioethanol obtained in the bioethanol production step S4 and the brown coal crushing step S22. The second gasification step S32 and the steam reforming step S33 are provided.

In the first gasification step S31, the bioethanol obtained in the bioethanol production step S4 obtained by fermenting the juice of old palm trees (OPT) and palm branches and leaves (OPF) is converted into ethanol gas through, for example, a vaporizer.
In the second gasification step S32, carbon monoxide and carbon dioxide are obtained by heating the powdered lignite obtained in the lignite crushing step S22 with a heater.

In the steam reforming step S33, the steam (high temperature steam) obtained in the energy generation step S16 and the methane generated in the methane production step (fermentation step) S17 using the separated water (POME) in the oil-water separation step S13, the first The ethanol gas obtained in the first gasification step S31, the carbon monoxide obtained in the second gasification step S32, and the like are reformed by a steam reforming method to generate hydrogen. The reaction to generate hydrogen from water vapor, hydrocarbon (ethanol, methanol) gas, and carbon monoxide is as follows.
(1) C _n H _m + nH ₂ O → nCO + (n + m / 2) H ₂
(2) CO + H ₂ O → CO ₂ + H ₂

In such a steam reforming step S33, the renewable heat energy obtained in the energy generation step S16 can be used as the heat energy for the reaction. Through the above steps, hydrogen can be produced efficiently and at extremely low cost by using unused biomass resources derived from the palm industry and lignite produced in the vicinity of palm palm plantations. The hydrogen thus obtained can be put into a liquefied state for easy transportation and used as a heat energy source or a raw material gas in a wide range of industries.

Next, the water electrolysis hydrogen generation process 16 will be described.
The water electrolysis hydrogen generation process 16 includes an electrolysis step S34 that electrolyzes water by the electric power generated by using the thermal energy obtained in the energy generation step S16. In this electrolysis step S34, hydrogen can be produced at extremely low cost by electrolyzing water using electric power, which is a renewable energy produced from unused biomass resources derived from the palm industry. The hydrogen thus obtained can be put into a liquefied state for easy transportation and used as a heat energy source or a raw material gas in a wide range of industries.

As described above, according to the method for producing hydrogen using the biomass resource of the present invention, palm branches and leaves (OPF), palm old trees (OPT), and empty fruit bunches (EFB), which have not been effectively used in the past, are used. , Simple incinerated palm coconut shell (PKS), palm fiber (Fiber), palm coconut effluent (POME) are used to produce methane and biomass, and surplus energy is used to generate steam. Since hydrogen is generated from the steam by the steam reforming method, it is possible to obtain hydrogen at extremely low cost without newly supplying raw materials and energy from the outside. In addition, since water is electrolyzed to generate hydrogen by electric power, which is a renewable energy using unused biomass resources derived from the palm industry, which has not been effectively used in the past, new raw materials and energy should be supplied from the outside. It is possible to obtain hydrogen at extremely low cost.

And by reusing unused biomass resources generated in the palm palm industry without being discharged as waste, it is possible to purify wastewater and suppress the generation of greenhouse gases, so palm palm farms that are suitable for environmental conservation. Contribute to the sustainable operation of.

1 Palm palm 2 Tree trunk 3 Palm branches and leaves (OPF: recycled raw material)
4 fruit 4A outer pericarp 4B flesh (middle pericarp)
4C palm coconut core (emissions)
6 Leaf (Rachis)
7 Petiole
10 Hydrogen production method using biomass resources (biomass resources and energy system using lignite)
11 Harvesting and sorting process 12 Semi-carbonization process 13 Palm oil production process 14 Biomass reformed coal production process 15 Steam reforming hydrogen production process 16 Water electrolysis hydrogen production process 17 Hydrogen production process

Claims (9)

In the palm oil production process of obtaining palm oil from palm palm trees, the separation process of obtaining recycled raw materials from palm palm trees, the semi-carbonized process of producing biomass semi-carbohydrate and bioethanol from the recycled raw materials, and the palm oil production process. It has a hydrogen production process in which methane is produced using the generated emissions and hydrogen is obtained by steam reforming together with the above-mentioned biomass.
The hydrogen production process is a method for producing hydrogen using biomass resources, which comprises using renewable energy generated by using the emissions generated in the palm oil production process as an operating energy source. The sorting process comprises a harvesting step of separating and harvesting the fruit cluster and the palm branches and leaves growing around the fruit cluster from the palm palm tree.
The semi-carbonization process includes a squeezing step of squeezing the palm branches and leaves and separating them into a squeezed liquid and a first solid residue, a bioethanol production step of fermenting the squeezed liquid to produce bioethanol, and the first. A semi-carbonization step of semi-carbonizing the solid residue to obtain a biomass semi-carbonized product is provided.
The palm oil production process includes a fruit removal step of removing fruits from the fruit bunches and separating them into empty fruit bunches after fruit removal, and squeezing the fruits into crude palm oil and a second solid residue. It comprises an oil squeezing step for separating and an oil-water separation step for obtaining palm oil and separated water by oil-water separation after adding water to the crude palm oil and suspending the oil.
The hydrogen production process is a first gasification step of gasifying the bioethanol, a methane production step of fermenting the separated water to produce methane, and the second solid residue obtained in the oil extraction step. Hydrogen is produced by a steam reforming method from an energy generation step of generating steam, electric power, and heat energy from palm coconut shells and palm fibers, and from the biomass gas, the methane, and the steam obtained in the energy generation step. The method for producing hydrogen using a biomass resource according to claim 1, further comprising a steam reformed hydrogen generation step for producing. The steam reformed hydrogen production step includes at least a reaction step of reacting the biomass gas and the methane with the steam, and a separation step of separating hydrogen generated by the reaction step from carbon monoxide and carbon dioxide. 2. The method for producing hydrogen using a biomass resource according to claim 2. The semi-carbonization process of hydrogen using the biomass resource according to claim 2 or 3, further comprising a compression molding step of compress-molding the biomass semi-carbide to pelletize it to obtain a solid biomass fuel. Production method. Biomass reforming including a lignite drying step of drying lignite, a lignite crushing step of crushing the dried lignite to obtain lignite powder, and a second gasification step of generating carbon monoxide from the lignite powder. With more lignite production process
The method for producing hydrogen using a biomass resource according to any one of claims 2 to 4, wherein the carbon monoxide is further added to the steam reformed hydrogen production step. The hydrogen using the biomass resource according to any one of claims 2 to 5, wherein the electric power or heat energy obtained in the energy generation step is used as an operating energy source in the steam reforming hydrogen generation step. Production method. Any of claims 2 to 6, wherein the hydrogen production process further includes a water electrolysis hydrogen production step of generating hydrogen by a water electrolysis method of electrolyzing water using the electric power obtained in the energy generation step. A method for producing hydrogen using the biomass resource described in item 1. As the palm branch leaf, the biomass resource according to any one of claims 2 to 7, wherein the petiole is used among the leaf part on which the palm leaf grows and the petiole forming the fruit bunch side of the leaf part was used. Hydrogen production method. The method for producing hydrogen using the biomass resource according to any one of claims 2 to 8, wherein in addition to the palm branches and leaves, the trunk of the palm palm tree is further supplied to the juice squeezing step. ..

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