CN115073266A - Device and process for preparing methanol based on coal - Google Patents
Device and process for preparing methanol based on coal Download PDFInfo
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- CN115073266A CN115073266A CN202210854463.9A CN202210854463A CN115073266A CN 115073266 A CN115073266 A CN 115073266A CN 202210854463 A CN202210854463 A CN 202210854463A CN 115073266 A CN115073266 A CN 115073266A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000003245 coal Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 57
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000001699 photocatalysis Effects 0.000 claims abstract description 34
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 26
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 57
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- FMMSEFNIWDFLKK-UHFFFAOYSA-N [O].OO Chemical compound [O].OO FMMSEFNIWDFLKK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0211—Peroxy compounds
- C01B13/0214—Hydrogen peroxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
A device and a process for preparing methanol based on coal belong to the technical field of liquid fuel preparation, can solve the problems of low energy utilization rate, serious pollution and the like in the prior art, and comprise a photocatalytic water decomposition system, CO 2 The device and the process can realize the fixation of carbon dioxide into methanol energy, reduce the consumption of coal resources, increase the utilization rate of the coal resources and carry out photolysisThe method for preparing hydrogen from water can reduce the energy consumption in the process.
Description
Technical Field
The invention belongs to the technical field of liquid fuel preparation, and particularly relates to a device and a process for preparing methanol based on coal.
Background
Because of the energy structure of lean oil, less gas and more coal, the energy consumption of China still takes fossil energy as the main energy in the next years. The proportion of the coal resources used by China is about 60%, the dependence on fossil energy can be reduced in the future, but the coal resources can be efficiently and cleanly utilized, and the development of the energy structure advantage of the coal in China is undoubtedly the most beneficial way for the future development of China. How to reduce the emission of carbon dioxide while scientifically utilizing coal resources or become an important subject and development direction of future research.
Except nuclear energy, the combustion heat value of hydrogen is higher than that of all fossil fuels and biofuels, and combustion products only contain water, so that other pollution gases cannot be generated. The development of hydrogen energy is wanted in the future, and the key points are three major pain points of high cost of hydrogen storage and transportation, large potential safety hazard and high investment of infrastructure with large occupied area of a hydrogenation station. The hydrogen production amount of 1L methanol is twice of that of 1L liquid hydrogen, the storage and transportation cost of methanol is low, the safety coefficient is high, and the methanol is used as an intermediate carrier to solve the problem of a fuel cell hydrogen supply chain, so that the hydrogen production method is a great direction for future development.
The problem of low utilization efficiency of coal resources exists in the coal-to-methanol industry at present, coal 2/3 for producing methanol is used for producing hydrogen through water gas shift and is finally converted into carbon dioxide to be discharged, and the preparation process has the advantages of high energy consumption, high carbon dioxide discharge amount, strict environment requirements on the change conditions of water gas, and high energy consumption. Therefore, even if the method is used as a way for clean utilization of coal, the defects of high energy consumption and low resource utilization rate in coal hydrogen production cannot be overcome.
The total pattern of the coal resources in China on the geographical distribution is more west and less east, and more north and less south. And is distributed in a reverse direction with the water resource distribution. The hydrogen production by water gas shift not only has high water resource consumption but also has serious pollution to water resources. The Shanxi province, inner Mongolia, Shaanxi province, Xinjiang, Guizhou, Ningxia and other six provinces (autonomous regions) have 82.8% of national coal resources, clean energy and traditional fossil energy are combined by utilizing the advantages of abundant solar energy and wind energy in the northwest region and abundant water resources in the southwest region, the traditional coal-to-hydrogen process is replaced by hydrogen prepared by photocatalytic water decomposition, and the emission of carbon dioxide and unnecessary energy consumption in the water gas hydrogen production process can be avoided. The prior hydrogen production process mainly comprises hydrogen production from fossil raw materials, hydrogen production from secondary gas and hydrogen production from water electrolysis, the pollution of hydrogen production from coal is serious, the hydrogen production from natural gas depends on imported natural gas, the subsequent purification technical requirement of hydrogen production from secondary gas is strict, and the hydrogen production from water electrolysis is difficult to start quickly or the hydrogen production speed cannot be adjusted quickly due to load change.
Disclosure of Invention
Aiming at the problems of low energy utilization rate, serious pollution and the like in the prior art, the invention provides a device and a process for preparing methanol based on coal.
The invention adopts the following technical scheme:
a device for preparing methanol based on coal comprises a photocatalytic decomposition water system and CO 2 The system comprises a reduction system, a gas regulation and control system and a methanol synthesis reaction system, wherein the photocatalytic decomposition water system comprises a photocatalytic hydrogen production device and a manganese dioxide catalytic hydrogen peroxide oxygen preparation device; CO 2 2 The reduction system comprises a coal pulverization device, a pulverized coal boiler and a gas purification and separation device; the gas regulation and control system comprises a hydrogen pressurizing device, an oxygen pressurizing device, a carbon monoxide pressurizing device and a gas mixing device; the methanol synthesis reaction system comprises a methanol synthesis tower and a rectification device.
Furthermore, the outlet of the coal pulverizing device is connected with the inlet of a pulverized coal boiler, one end of the photocatalytic hydrogen production device is connected with the inlet of the manganese dioxide catalyzed hydrogen peroxide oxygen preparation device, the outlet of the manganese dioxide catalyzed hydrogen peroxide oxygen preparation device is connected with the inlet of the pulverized coal boiler through an oxygen pressurizing device and an oxygen flow control valve, the outlet of the pulverized coal boiler is connected with the inlet of a gas purification and separation device, the outlet of the gas purification and separation device is connected with the inlet of a gas mixing device through a carbon monoxide pressurizing device and a carbon monoxide flow control valve, the other end of the photocatalytic hydrogen production device is connected with the inlet of the gas mixing device through a hydrogen pressurizing device and a hydrogen flow control valve, the outlet of the gas mixing device is connected with the inlet of a methanol synthesis tower, and the outlet of the methanol synthesis tower is connected with the inlet of a rectifying device.
A process for preparing methanol based on coal comprises the following steps:
firstly, crushing pulverized coal by a coal pulverizing device, and feeding the pulverized coal into a pulverized coal boiler;
secondly, decomposing water in a photocatalytic decomposition water system under the action of a catalyst by light to prepare hydrogen, and feeding the hydrogen into a gas mixing device;
step three, preparing oxygen by catalyzing hydrogen peroxide with a catalyst in a photocatalytic decomposition water system, and introducing the oxygen into a pulverized coal boiler;
fourthly, in a pulverized coal boiler, carbon dioxide reduction is carried out to prepare carbon monoxide, and the generated gas is introduced into a gas purification and separation device and then is introduced into a gas mixing device;
and fifthly, introducing the mixed gas in the gas mixing device into a methanol synthesis tower to synthesize methanol.
Further, the pulverized coal crushing particle size in the first step is 10 mm.
Further, in the pulverized coal boiler, carbon dioxide and oxygen are introduced in an intermittent and continuous mode, and after the reaction temperature is 950 ℃, the carbon dioxide and the oxygen are continuously introduced, and then the temperature is raised to 1200 ℃.
Further, the hydrogen-carbon ratio in the gas mixing device is 2, and the carbon is a mixture of carbon monoxide and carbon dioxide, wherein the volume ratio of the carbon monoxide in the mixture is more than 90%.
Further, Pt/TiO is adopted for preparing hydrogen by decomposing water through photocatalysis 2 The (anatase) mixture as catalyst was dispersed in a quartz reactor and sealed under magnetic stirring at room temperature while catalytically decomposing with a 500W mercury lamp.
Further, the catalyst for preparing hydrogen by photocatalytic water decomposition is prepared by an in-situ light deposition method.
The invention adopts the system for preparing hydrogen and hydrogen peroxide by decomposing water by photocatalysis, the hydrogen and the hydrogen peroxide are automatically separated, the equipment investment in the process of gas separation is avoided, the hydrogen can be produced in large scale, and the dangerous and energy-intensive process is not needed.
The carbon dioxide is reduced at high temperature by carbon to prepare the carbon monoxide, all the used raw materials are low-cost industrial products, firstly, the crushed coal powder is heated, then the carbon dioxide is introduced to fully react with oxygen, and then the gas prepared by the reaction is subjected to a gas purification device to obtain the carbon monoxide.
Carbon dioxide is used for preparing carbon monoxide, and methanol is synthesized and prepared by combining a photolysis hydrogen production technology, the methanol is used as liquid fuel (energy storage medium) to provide hydrogen for a hydrogen fuel cell, renewable energy is combined with traditional fossil energy, the utilization efficiency of coal resources is improved, and the consumption of the fossil energy is reduced. The method has great significance for solving the energy problem of China, changing the current situation of energy structure and economic sustainable development.
The basic reaction principle and side reactions are as follows:
the photocatalytic decomposition water system adopts light to decompose water under the action of a catalyst to prepare hydrogen, and the generated gas is only hydrogen without a gas separation process.
The hydrogen peroxide generated by the photocatalytic decomposition water system is used for preparing oxygen, the prepared oxygen and carbon dioxide are introduced into the reaction device simultaneously in an intermittent introduction mode, and the heat required by reduction can be provided due to the fact that the introduced oxygen reacts with the pulverized coal while the sufficient reduction of the carbon dioxide is guaranteed.
The invention has the following beneficial effects:
1. the hydrogen is prepared by decomposing water by photocatalysis, the generated gas is only hydrogen, the gas separation process can be omitted, the cost is reduced, and the consumption of coal resources can be greatly reduced compared with the conventional water gas hydrogen preparation.
2. The hydrogen peroxide prepared by photocatalysis can be prepared by manganese dioxide catalysis, oxygen and carbon dioxide are mixed and introduced into a carbon dioxide reduction area, and heat is provided by the reaction of the oxygen and coal powder.
3. Carbon dioxide is adopted to prepare carbon monoxide through reduction, all raw materials are low-price industrial products, carbon dioxide is consumed in the preparation process, the utilization rate of coal is improved, and double benefits of energy conservation and environmental protection are achieved.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention;
wherein: 1-coal pulverizing equipment; 2-pulverized coal fired boiler; 3-a gas purification and separation device; 4-a photocatalytic hydrogen production device; 5-manganese dioxide catalysis hydrogen peroxide preparation oxygen device; 6-oxygen pressurizing device; 7-an oxygen flow control valve; 8-a hydrogen pressurization device; 9-hydrogen flow control valve; 10-a carbon monoxide pressurizing device; 11-a carbon monoxide flow control valve; 12-a gas mixing device; 13-a methanol synthesis column; 14-rectification device.
Detailed Description
The invention is further described with reference to the accompanying drawings and examples.
The photocatalytic hydrogen production apparatus in the present invention is disclosed in patent publication No. 2018107537792. The methanol synthesis column is referred to as published apparatus 2020221333053. The remaining devices are well known to those skilled in the art.
A process for preparing methanol based on coal comprises the following steps:
firstly, crushing pulverized coal by a coal pulverizing device, and feeding the pulverized coal into a pulverized coal boiler;
secondly, decomposing water in a photocatalytic decomposition water system under the action of a catalyst by light to prepare hydrogen, and feeding the hydrogen into a gas mixing device;
step three, preparing oxygen by catalyzing hydrogen peroxide with a catalyst in a photocatalytic decomposition water system, and introducing the oxygen into a pulverized coal boiler;
fourthly, in a pulverized coal boiler, carbon dioxide reduction is carried out to prepare carbon monoxide, and the generated gas is introduced into a gas purification and separation device and then is introduced into a gas mixing device;
and fifthly, introducing the mixed gas in the gas mixing device into a methanol synthesis tower to synthesize methanol.
In the first step, the pulverized coal has a crushed particle size of 10 mm.
In the pulverized coal boiler, carbon dioxide and oxygen are introduced in an intermittent and continuous mode, the reaction temperature is 950 ℃, then the carbon dioxide and the oxygen are continuously introduced, and then the temperature is raised to 1200 ℃.
The hydrogen-carbon ratio in the gas mixing device is 2, and carbon is a mixture of carbon monoxide and carbon dioxide, wherein the carbon monoxide accounts for more than 90% of the volume ratio of the mixture.
The Pt/TiO is adopted for preparing hydrogen by photocatalytic water decomposition 2 The (anatase) mixture as catalyst was dispersed in a quartz reactor and sealed under magnetic stirring at room temperature while catalytically decomposing with a 500W mercury lamp.
The catalyst for preparing hydrogen by photocatalytic water decomposition is prepared by an in-situ light deposition method.
The preparation process of the catalyst for preparing hydrogen by photocatalytic water decomposition comprises the following steps: slowly adding the titanium tetrachloride solution into the ammonia solution until the pH value is about 8, wherein the molar concentration ratio of the titanium tetrachloride to the ammonia solution is 2: 5, washing the obtained white precipitate with distilled water after centrifugation until chloride ions can not be detected in the washing liquid, drying the precipitate, and calcining at 400 ℃ for 2.5 hours to prepare titanium dioxide; with H 2 PtCl 6 (Pt 1 wt%) as a precursor, a methanol solution with the mass concentration of 10% as an electron donor, preparing Pt nano particles by adopting an in-situ light precipitation method, and centrifugally collecting a sample after ultraviolet irradiation for one hour. Drying at 90 ℃ for 24h removed residual methanol and water.
The Pt/TiO is adopted for preparing hydrogen by photocatalytic water decomposition 2 (anatase) mixture is used as a catalyst, and the mass ratio of (anatase) mixture is 1: 20 proportion the hybrid and deionized water are placed in a quartz reactor and sealed by a rubber diaphragm, air in the reactor is removed by blowing argon for 30min, and then the catalyst is decomposed by irradiating a mercury lamp of 500W while magnetically stirring at room temperature.
The manganese dioxide is used for catalyzing hydrogen peroxide to decompose to prepare oxygen, industrial manganese dioxide is used as a catalyst, and the hydrogen peroxide prepared by photocatalytic decomposition is catalyzed to decompose to prepare oxygen.
Claims (8)
1. The utility model provides a device based on coal preparation methyl alcohol which characterized in that: comprises a photocatalytic water decomposition system and CO 2 The system comprises a reduction system, a gas regulation and control system and a methanol synthesis reaction system, wherein the photocatalytic decomposition water system comprises a photocatalytic hydrogen production device and a manganese dioxide catalytic hydrogen peroxide oxygen preparation device; CO 2 2 The reduction system comprises a coal pulverization device, a pulverized coal boiler and a gas purification and separation device; the gas regulation and control system comprises a hydrogen pressurizing device, an oxygen pressurizing device, a carbon monoxide pressurizing device and a gas mixing device; the methanol synthesis reaction system comprises a methanol synthesis tower and a rectification device.
2. The coal-based methanol plant as claimed in claim 1, wherein: the outlet of the coal pulverizing device is connected with the inlet of a pulverized coal boiler, one end of the photocatalytic hydrogen production device is connected with the inlet of the manganese dioxide catalyzed hydrogen peroxide oxygen preparation device, the outlet of the manganese dioxide catalyzed hydrogen peroxide oxygen preparation device is connected with the inlet of the pulverized coal boiler through an oxygen pressurizing device and an oxygen flow control valve, the outlet of the pulverized coal boiler is connected with the inlet of a gas purification and separation device, the outlet of the gas purification and separation device is connected with the inlet of a gas mixing device through a carbon monoxide pressurizing device and a carbon monoxide flow control valve, the other end of the photocatalytic hydrogen production device is connected with the inlet of the gas mixing device through a hydrogen pressurizing device and a hydrogen flow control valve, the outlet of the gas mixing device is connected with the inlet of a methanol synthesis tower, and the outlet of the methanol synthesis tower is connected with the inlet of a rectification device.
3. A process for the preparation of methanol using the apparatus of claim 1 or 2, characterized in that: the method comprises the following steps:
firstly, crushing pulverized coal by a coal pulverizing device, and feeding the pulverized coal into a pulverized coal boiler;
secondly, decomposing water in a photocatalytic decomposition water system under the action of a catalyst by light to prepare hydrogen, and feeding the hydrogen into a gas mixing device;
step three, preparing oxygen by catalyzing hydrogen peroxide with a catalyst in a photocatalytic decomposition water system, and introducing the oxygen into a pulverized coal boiler;
fourthly, in a pulverized coal boiler, carbon dioxide reduction is carried out to prepare carbon monoxide, and the generated gas is introduced into a gas purification and separation device and then is introduced into a gas mixing device;
and fifthly, introducing the mixed gas in the gas mixing device into a methanol synthesis tower to synthesize methanol.
4. The coal-based process for methanol production according to claim 3, wherein: in the first step, the pulverized coal has a crushed particle size of 10 mm.
5. The coal-based process for methanol production according to claim 3, wherein: in the pulverized coal boiler, carbon dioxide and oxygen are introduced in an intermittent and continuous mode, the reaction temperature is 950 ℃, then the carbon dioxide and the oxygen are continuously introduced, and then the temperature is raised to 1200 ℃.
6. The coal-based process for methanol production according to claim 3, wherein: the hydrogen-carbon ratio in the gas mixing device is 2, and carbon is a mixture of carbon monoxide and carbon dioxide, wherein the carbon monoxide accounts for more than 90% of the volume ratio of the mixture.
7. The coal-based process for methanol production according to claim 3, wherein: the Pt/TiO is adopted for preparing hydrogen by photocatalytic water decomposition 2 The mixture was used as a catalyst, dispersed in a quartz reactor, and subjected to catalytic decomposition by irradiation with a 500W mercury lamp while being magnetically stirred at room temperature under sealed conditions to produce hydrogen.
8. The coal-based process for methanol production according to claim 3, wherein: the catalyst for preparing hydrogen by photocatalytic water decomposition is prepared by an in-situ light deposition method.
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| CN112457159A (en) * | 2019-09-09 | 2021-03-09 | 中国科学院大连化学物理研究所 | Device for preparing methanol based on coal and methanol preparation process |
| CN113860991A (en) * | 2021-10-08 | 2021-12-31 | 华陆工程科技有限责任公司 | Ammonia and alcohol co-production method for realizing low-carbon emission by combining photocatalysis with coal gas production |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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