JPH11188262A - Apparatus for producing methanol utilizing biomass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain H2 at a low cost and to fix CO2 with the H2 . SOLUTION: Evolved gas contg. CH4 and CO2 is generated by the anaerobic fermentation of a biomass in a biomass treatment part 2 and it is sent to a methane separation-concentration part 4. The CH4 is purified from the evolved gas by passing through a methane separating-trating unit 4 and it is decomposed into carbon and H2 in the presence of a catalyst in a methane decomposition part 6. The generated H2 is sent to a methanol production part 8 and CO2 is allowed to react with the H2 in the presence of a catalyst to synthesize methanol. The resultant gaseous methanol is condensed and separated from steam by passing through a condensation part 10, liq. methanol is obtd. and the CO2 is fixed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to general fields of environmental control such as sewage treatment, smoke control, garbage disposal, livestock waste, etc., carbon black production, methanol production, dimethyl ether production, gasoline, and the like. It relates to the field of manufacturing utilization.

[0002]

2. Description of the Related Art Atmospheric carbon dioxide (CO)_Two) And power generation
Emitted from plants, steelworks, heavy chemical plants, etc.
_TwoIs one of the methods of fixing and recycling resources at the emission source.
Hydrogen (H _Two) CO under atmosphere_TwoTo methanol
An alternative method has been devised. The conversion method is air or
From exhaust gas to CO_TwoTo separate CO_TwoSeparation device and its separation
CO_TwoTo concentrate CO_TwoConcentrator, CO_TwoAnd H_TwoThe catalyst
CO that reacts in the presence to synthesize methanol_Two/ H_TwoAnti
It consists of a response device.

[0003]

A method for obtaining H ₂ necessary for converting CO ₂ into methanol and fixing it, for example, by electrolysis of water, use of solar cell power generation, decomposition of methane (CH ₄ ), etc. Although various CO ₂ fixing methods have been proposed, H ₂ is very expensive at present and has not been commercialized.

[0004] Therefore, the present invention provides a CO_TwoTo fix
H required for_TwoAt low cost, and its H _TwoUsing CO_TwoTo
It is intended to convert to methanol and fix it
is there.

[0005]

Means for Solving the Problems Biomass according to the present invention
(Organic waste) One aspect of the methanol production system that utilizes methanol is a methane generation section that generates methane and carbon dioxide by anaerobic fermentation of biomass, and methane generated in the methane generation section is decomposed into carbon and hydrogen using a catalyst. And a methanol producing section for synthesizing methanol by reacting carbon dioxide with hydrogen generated in the methane decomposition section using a catalyst.

[0006] By obtaining CH ₄ from the generated gas obtained by anaerobic fermentation of biomass with bacteria and decomposing the CH ₄ in the presence of a catalyst, H ₂ required for methanol production can be obtained.
Get. The H ₂ is reacted with CO ₂ to obtain methanol. By decomposing CH ₄ obtained by anaerobic fermentation of biomass in the presence of a catalyst, H ₂ occupying 90% or more of the energy required for methanol production can be obtained.
H ₂ can be obtained at low cost, and the apparatus body can be configured at low cost.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In another embodiment of the biomass-using methanol production apparatus according to the present invention, a methane / carbon dioxide separation section for separating methane and carbon dioxide generated in a methane generation section, and a methane / carbon dioxide separation section And a methanol producing section that reacts the produced carbon dioxide with hydrogen produced in the methane decomposition section in the presence of a catalyst to produce methanol.
Since it is supplied from the carbon dioxide separation unit, CO
It is not necessary to supply ₂ .

[0008] In still another embodiment of the biomass-utilizing methanol production apparatus according to the present invention, a hydrogen combustion section that burns a part of the hydrogen generated in the methane decomposition section, And a reaction heat transfer unit that supplies the heat to the methane generation unit and the methane decomposition unit.The heat energy generated in the hydrogen combustion unit is used for the heat energy required in the methane decomposition unit, eliminating the need to supply heat energy from the outside. And contribute to cost reduction. If hydrogen remains even when used in the production of methanol or further used in the hydrogen combustion section, it can be released outside the system and used as fuel.

[0009]

FIG. 1 is a block diagram showing one embodiment. Ma
First, the configuration will be described. Paper, beer waste, beer
Biomass such as lees and garbage is removed by bacteria in an anaerobic fermenter.
Decompose, CH_FourAnd CO_TwoOrganic waste treatment department (meaning
Tongue generating part) 2 is provided. Organic waste treatment section 2
Is connected to the methane separation / concentration unit 4
Is the separation / concentration unit 4 a gas generated in the organic waste treatment unit 2?
Impurities such as sulfur components by desulfurization tower and zeolite catalyst
After removing CO 2 through a monoethanolamine solution.
_TwoTo remove CH_FourIs separated and concentrated. Methane separation and concentration
The methane decomposition section 6 is connected to the section 4 so that the methane
The solution section 6 includes, for example, SiO_TwoAnd Al_TwoO_ThreeNi as a carrier
Equipped with a catalyst such as Co catalyst, from the methane separation / concentration unit 4
CH_FourTo carbon and H_TwoDecompose into In the methane decomposition section 6,
Methanol production section 8 is connected and produces methanol
The portion 8 includes, for example, SiO _TwoAnd Al_TwoO_ThreeNi-C as a carrier
o generated by the methane decomposition section 6
_TwoTo CO_TwoTo synthesize methanol. Methaneau
The methanol synthesized in the methanol production section 8 is condensed and methanol
Water (H_TwoCondensation to separate O)
A unit 10 is provided. Here, the organic waste treatment unit 2
And the methane separation / concentration unit 4 constitute a methane generation unit.

Next, the operation will be described. The biomass is put into the anaerobic fermenter in the organic waste treatment section 2 together with bacteria such as methane bacteria. In the organic waste treatment unit 2, generated gas containing CH ₄ and CO ₂ is generated by anaerobic fermentation of biomass and the like, and the generated gas is sent to the methane separation / concentration unit 4. CH ₄ is purified from the generated gas by passing through a methane separation / treatment device 4, and the CH ₄ is decomposed into carbon (C) and H ₂ in a methane decomposition section 6 in the presence of a catalyst. C precipitates as solid carbon black. CH ₄ → C + 2H ₂ +90.1 kJ / mol

The H ₂ generated in the methane decomposition section 6 is sent to a methanol production section 8 where CO ₂ and H ₂ are reacted in the presence of a catalyst to synthesize methanol (CH ₃ OH). CO ₂ + 3H ₂ → CH ₃ OH + H ₂ O-60.1 kJ / mol The obtained gaseous methanol is condensed by passing through the condensing section 10 and separated from water vapor (H ₂ O) to obtain liquid methanol. .

Since the carbon obtained in the methane decomposition section 6 can be used as industrial carbon black, it is possible to convert what used to be a fossil fuel as a raw material into what is a waste as a raw material. Can be saved. A part of the carbon obtained in the methane decomposition section 6 contains fullerenes and carbon nanotubes having high added value, and can be used as by-products by purification.

FIG. 2 shows a block diagram of another embodiment.
First, the configuration will be described. The organic waste treatment section 2 and the methane separation / treatment device 4 are the same as those in FIG. In the methane separation / concentration unit 4, carbon monoxide is produced by reacting CH ₄ concentrated in the methane separation / concentration unit ₄ with CO _2.
Methane / carbon dioxide reaction section 12 decomposing into (CO) and H ₂
Is connected. A methane / carbon dioxide reaction unit 12 is connected to a methanol production unit 14 for reacting CO and H ₂ to synthesize methanol.
A catalyst for methyl alcohol synthesis such as a chromium oxide catalyst is provided.

Next, the operation will be described. The biomass is put into the anaerobic fermenter in the organic waste treatment section 2 together with bacteria such as methane bacteria. In the organic waste treatment unit 2, generated gas containing CH ₄ and CO ₂ is generated by anaerobic fermentation of biomass and the like, and the generated gas is sent to the methane separation / concentration unit 4. CH ₄ is purified from the generated gas by passing through a methane separation / treatment device 4, and the CH ₄ is decomposed into CO and H ₂ by reacting the CH ₄ with carbon dioxide in the presence of a catalyst in a methane / carbon dioxide reaction section 12. I do. CH ₄ + CO ₂ → 2CO + 2H ₂ +251 kJ / mol

The CO and H ₂ generated in the methane / carbon dioxide reaction section 12 are sent to a methanol production section 14, where CO and H ₂ are reacted in the presence of a catalyst to synthesize methanol (CH ₃ OH). CO + 2H ₂ → CH ₃ OH-86.1 kJ / mol Thereafter, the obtained gaseous methanol is condensed to obtain liquid methanol.

Although CO ₂ used in the methane / carbon dioxide reaction section 12 is supplied from outside the system, CO ₂ generated in the anaerobic fermenter in the organic waste treatment section 2 is used in the methane / carbon dioxide reaction section 12. It is preferably used as a part of ₂ . As a result, CO ₂ generated from the inside of the system can also be fixed.

FIG. 3 shows a block diagram of still another embodiment. The organic waste treatment section 2 is the same as that in FIG.
The organic waste treatment section 2 has a methane / carbon dioxide separation section 1
6 is connected, and the gas generated in the organic waste treatment section 2 is converted into C using, for example, the adsorption / desorption of zeolite.
Separate into H ₄ and CO ₂ . This separation utilizes a difference in adsorption conditions such as temperature, pressure and adsorption speed to adsorb only one of CH ₄ and CO ₂ , and then desorbs the adsorbed components at a high temperature or pressure. It can be carried out by repeating the steps. The methane decomposition section 6 is connected to the methane / carbon dioxide separation section 16. The methane decomposition section is the same as in FIG. The methane decomposition section 6 is connected to a methanol production section 8. For example, the methanol production unit 8 may include Cu / ZnO, Cu / ZnO / Al ₂ O ₃ , C
a catalyst such as u / ZnO / Al ₂ O ₃ / Cr ₂ O ₃ , and reacts a part of H ₂ generated in the methane decomposition section 6 with CO ₂ separated in the methane / carbon dioxide separation section 16 to form methanol. Generate Steam generated in methanol production unit 8
A condensing section 12 for condensing (H ₂ O) is provided.

Next, the operation will be described. The biomass is introduced into the anaerobic fermenter in the organic waste treatment section 2 containing methane bacteria. In the organic waste treatment section 2, a gas containing CH ₄ and CO ₂ is generated by anaerobic fermentation of biomass, and the gas is separated into CH ₄ and CO ₂ by passing the gas through a methane / carbon dioxide separation section 16, The CH ₄ is decomposed into carbon (C) and H ₂ in the methane decomposition section 6 in the presence of a catalyst.
Carbon precipitates as solid carbon black. CH ₄ → C + 2H ₂ +90.1 kJ / mol

The CO ₂ separated in the methane / carbon dioxide separation section 16 and the H ₂ generated in the methane decomposition section 6 are sent to a methanol production section 8, where CO ₂ and H ₂ are reacted in the presence of a catalyst to produce methanol (CH _3). OH). CO ₂ + 3H ₂ → CH ₃ OH + H ₂ O-60.1 kJ / mol The obtained gaseous methanol is condensed by passing through the condensing section 12 and separated from water vapor (H ₂ O) to obtain liquid methanol. .

FIG. 4 shows a block diagram of still another embodiment. The organic waste treatment section 2 is the same as that in FIG.
The organic waste treatment section 2 has a methane / carbon dioxide separation section 1
6 is connected, and separates gas generated in the organic waste treatment section 2 into CH ₄ and CO ₂ . The methane decomposition section 6 is connected to the methane / carbon dioxide separation section 16. The methane decomposition section is the same as in FIG. In the methane decomposition section 6,
The methanol production section 8 and the hydrogen combustion section 14 are connected. The hydrogen combustion unit 14 burns a part of the hydrogen decomposed in the methane decomposition unit 6 and supplies the obtained combustion heat to the organic waste treatment unit 2 and the methane decomposition unit 6 by the reaction heat transfer unit. The reaction heat transfer section is, for example, a pipe tube, and the hydrogen combustion section 1
The combustion heat generated in step 4 is accumulated, and the accumulated heat is transmitted. The methanol production unit 8 is the same as that shown in FIG. 3, and reacts a part of H ₂ generated in the methane decomposition unit 6 with CO ₂ separated in the methane / carbon dioxide separation unit 16 to produce methanol. A condensing unit 12 for condensing steam (H ₂ O) generated in the methanol production unit 8 is provided.

Next, the operation will be described. The biomass is introduced into the anaerobic fermenter in the organic waste treatment section 2 containing methane bacteria. In the organic waste treatment section 2, a gas containing CH ₄ and CO ₂ is generated by anaerobic fermentation of biomass, and the gas is separated into CH ₄ and CO ₂ by passing the gas through a methane / carbon dioxide separation section 16, The CH ₄ is decomposed into carbon (C) and H ₂ in the methane decomposition section 6 in the presence of a catalyst.
Carbon precipitates as solid carbon black. CH ₄ → C + 2H ₂ +90.1 kJ / mol

A part of the H ₂ separated in the methane decomposition section 6 is sent to a hydrogen combustion section 14 for combustion. The combustion heat is used as a heat source for the organic waste treatment section 2 and the methane decomposition section 6. H ₂ + (1/2) O ₂ → H ₂ O-285 kJ / mol

The CO ₂ separated in the methane / carbon dioxide separation section 16 and the H ₂ generated in the methane decomposition section 6 are sent to a methanol production section 8, where CO ₂ and H ₂ are reacted in the presence of a catalyst to produce methanol (CH ₃ OH). CO ₂ + 3H ₂ → CH ₃ OH + H ₂ O-60.1 kJ / mol The obtained gaseous methanol is condensed by passing through the condensing section 12 and separated from water vapor (H ₂ O) to obtain liquid methanol. .

Since the heat of combustion generated in the hydrogen combustion section 14 is led to the organic waste treatment section 2 and the methane decomposition section 6, the anaerobic fermenter of the organic waste treatment section 2 is heated to promote the biomass fermentation. Energy can be reduced, the heat of the endothermic reaction of the methane decomposition section 6 can be supplemented, and the cost can be reduced.

In the embodiment shown in FIGS. 3 and 4, all the CO ₂ used in the methanol production section 8 is supplied from the methane / carbon dioxide separation section 16 so that all the CO ₂ generated in the apparatus system is removed. It can be immobilized in the methanol production section 8. CO ₂ used in methanol production section 8
In the case where only CO ₂ supplied from the methane / carbon dioxide separation unit 16 is insufficient, it is preferable to supply CO ₂ from outside.

In the embodiment shown in FIGS. 1 to 4, CO ₂ which is a greenhouse gas, which is one of the causes of global warming, can be immobilized in a large amount, thereby contributing to the global environment. it can. Since the carbon obtained in the methane decomposition section 6 can be used as industrial carbon black,
Conventionally, fossil fuel-based fuel can be converted to biomass-based fuel, which can contribute to resource saving. A part of the carbon obtained in the methane decomposition section 6 may contain high value-added fullerenes and carbon nanotubes, and can be used as a by-product by purification.

It is preferable to provide a reaction heat transfer section for guiding the reaction heat generated in the methanol production section 14 to the organic waste treatment section 2. As a result, the energy for heating the biomass fermenter to promote the biomass fermentation can be reduced, and the cost can be reduced.
Further, it is preferable to include a reaction heat utilization power generation unit that converts reaction heat generated in the methanol production unit 8 and the hydrogen combustion unit 14 into electric power. As a result, a part of the power for operating the device can be covered, and the cost can be reduced. The resulting methanol can be converted to gasoline, which can contribute to saving fossil fuel resources.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments, and various changes may be made within the scope of the present invention described in the appended claims. Can be. Examples of embodiments of the present invention will be illustrated below.

(1) A methane generating section for generating methane and carbon dioxide by anaerobic fermentation of biomass, a methane decomposing section for decomposing methane generated in the methane generating section into carbon and hydrogen using a catalyst, A methanol production section for synthesizing methanol by reacting carbon and hydrogen generated in the methane decomposition section using a catalyst, and a system internal carbon dioxide supply section for guiding carbon dioxide generated in the methane generation section to the methanol production section And a biomass-using methanol production apparatus, comprising:

(2) A methane generating section for generating methane and carbon dioxide by anaerobic fermentation of biomass, a methane decomposing section for decomposing methane generated in the methane generating section into carbon and hydrogen using a catalyst, A methanol production section that synthesizes methanol by reacting carbon and hydrogen generated in the methane decomposition section using a catalyst, and a reaction heat transfer section that guides reaction heat in the methanol production section to the methane generation section. An apparatus for producing methanol using biomass, comprising:

(3) A methane generating section for generating methane and carbon dioxide by anaerobic fermentation of biomass, a methane decomposing section for decomposing methane generated in the methane generating section into carbon and hydrogen using a catalyst, A methanol production unit that synthesizes methanol by reacting carbon and hydrogen generated in the methane decomposition unit using a catalyst, and a reaction heat utilization power generation unit that recovers reaction heat in the methanol production unit as electric power,
An apparatus for producing methanol using biomass, comprising:

(4) A methane generator for generating methane and carbon dioxide by anaerobic fermentation of biomass, and a methane generator for separating methane and carbon dioxide generated in the methane generator.
A carbon dioxide separation unit, a methane decomposition unit that decomposes methane separated in the methane / carbon dioxide separation unit into carbon and hydrogen in the presence of a catalyst, and a carbon dioxide and the methane decomposition unit separated in the methane / carbon dioxide separation unit A methanol production unit that produces methanol by reacting hydrogen produced in the presence of a catalyst, and a reaction heat transfer unit that supplies heat generated in the methanol production unit to the methane generation unit and the methane decomposition unit. An apparatus for producing methanol using biomass, comprising:

(5) A methane generator for generating methane and carbon dioxide by anaerobic fermentation of biomass, and a methane generator for separating methane and carbon dioxide generated in the methane generator.
A carbon dioxide separation unit, a methane decomposition unit that decomposes methane separated in the methane / carbon dioxide separation unit into carbon and hydrogen in the presence of a catalyst, and a carbon dioxide and the methane decomposition unit separated in the methane / carbon dioxide separation unit A methanol production unit that produces methanol by reacting the hydrogen produced in the presence of a catalyst, and a reaction heat utilization power generation unit that recovers heat generated in the methanol production unit as electric power, Biomass utilizing methanol production equipment.

(6) A methane generator for generating methane and carbon dioxide by anaerobic fermentation of biomass, and a methane generator for separating methane and carbon dioxide generated in the methane generator.
A carbon dioxide separation unit, a methane decomposition unit that decomposes methane separated in the methane / carbon dioxide separation unit into carbon and hydrogen in the presence of a catalyst, and a hydrogen combustion unit that burns a part of the hydrogen generated in the methane decomposition unit And a methanol producing unit for producing methanol by reacting carbon dioxide separated in the methane / carbon dioxide separation unit with a part of hydrogen generated in the methane decomposition unit in the presence of a catalyst, and generated in the hydrogen combustion unit. A reaction heat transfer unit that supplies the generated heat to the methane generation unit and the methane decomposition unit, and a reaction heat utilization power generation unit that recovers a part of the heat generated in the hydrogen combustion unit as electric power. Characteristic biomass-using methanol production equipment.

(7) A methane generator for generating methane and carbon dioxide by anaerobic fermentation of biomass, and a methane generator for separating methane and carbon dioxide generated in the methane generator.
A carbon dioxide separation unit, a methane decomposition unit that decomposes methane separated in the methane / carbon dioxide separation unit into carbon and hydrogen in the presence of a catalyst, and a hydrogen combustion unit that burns a part of the hydrogen generated in the methane decomposition unit And a methanol production unit that produces methanol by reacting carbon dioxide separated in the methane / carbon dioxide separation unit and a part of hydrogen generated in the methane decomposition unit in the presence of a catalyst, and the hydrogen combustion unit and A biomass-based methanol production apparatus, comprising: a reaction heat transfer section that supplies heat generated in a methanol production section to the methane generation section and the methane decomposition section.

(8) A methane generating section for generating methane and carbon dioxide by anaerobic fermentation of biomass, and a methane generating section for separating methane and carbon dioxide generated in the methane generating section.
A carbon dioxide separation unit, a methane decomposition unit that decomposes methane separated in the methane / carbon dioxide separation unit into carbon and hydrogen in the presence of a catalyst, and a hydrogen combustion unit that burns a part of the hydrogen generated in the methane decomposition unit And a methanol producing unit for producing methanol by reacting carbon dioxide separated in the methane / carbon dioxide separation unit with a part of hydrogen generated in the methane decomposition unit in the presence of a catalyst, and generated in the hydrogen combustion unit. A reaction heat transfer unit that supplies the generated heat to the methane generation unit and the methane decomposition unit, and a reaction heat utilization power generation unit that recovers heat generated in the methanol production unit as electric power. Biomass methanol production equipment.

[0037]

According to the present invention, biomass is subjected to anaerobic fermentation.
CH_FourAnd CO_TwoMethane generating section and methane generating
CH generated in the part_FourWith carbon and H_TwoDecompose into
Methane decomposition section, CO_TwoAnd H generated in the methane decomposition section_TwoWhen
Reacts with a catalyst to produce methanol
Production using biomass
Biomass obtained by anaerobic fermentation with bacteria
Generated gas from CH _FourAnd get that CH_FourThe catalyst present
By disassembling below_Two, So H_TwoInexpensive
I can do it, H_TwoTo CO_TwoTo produce methanol
And CO_TwoCan be fixed, and the device body is inexpensive
Can be configured. Furthermore, it is generated in the methane decomposition section
H_TwoEquipped with a hydrogen combustion section that burns
The generated combustion heat will be led to the methane generation section and methane decomposition section
Heat the methane generation section and methane decomposition section
Energy can be supplemented and costs can be reduced.
Can be.

[Brief description of the drawings]

FIG. 1 is a block diagram of one embodiment.

FIG. 2 is a block diagram of another embodiment.

FIG. 3 is a block diagram of still another embodiment.

FIG. 4 is a block diagram of still another embodiment.

[Explanation of symbols]

 2 Biomass treatment section 4 Methane separation / concentration section 6 Methane decomposition section 8 Methanol production section 10 Condenser

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 31/04 C12P 5/02 C12P 5/02 C07B 61/00 300 // C07B 61/00 300 B09B 3/00 ZABC (C12P 5/02 C12R 1:01)

Claims (3)

[Claims] 1. A methane generating unit for generating methane and carbon dioxide by anaerobic fermentation of biomass, a methane decomposing unit for decomposing methane generated in the methane generating unit into carbon and hydrogen using a catalyst, A biomass-utilizing methanol production apparatus, comprising: a methanol production section that reacts hydrogen produced in the methane decomposition section with a catalyst using a catalyst to synthesize methanol. 2. A methane generating section for generating methane and carbon dioxide by anaerobic fermentation of biomass, a methane / carbon dioxide separating section for separating methane and carbon dioxide generated in the methane generating section, A methane decomposition section that decomposes the methane separated in the carbon separation section into carbon and hydrogen in the presence of a catalyst, and converts the carbon dioxide separated in the methane / carbon dioxide separation section and the hydrogen generated in the methane decomposition section in the presence of a catalyst. A biomass-utilizing methanol production apparatus, comprising: a methanol production unit for producing methanol by reacting. 3. A hydrogen combustion section for burning a part of the hydrogen generated in the methane decomposition section, and a reaction heat transfer section for supplying heat generated in the hydrogen combustion section to the methane generation section and the methane decomposition section. The biomass-utilizing methanol production apparatus according to claim 1 or 2, further comprising: