CN108360011A - Ammonia electrolytic hydrogen production is used for the system and method for coal liquefaction - Google Patents
Ammonia electrolytic hydrogen production is used for the system and method for coal liquefaction Download PDFInfo
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- CN108360011A CN108360011A CN201810317907.9A CN201810317907A CN108360011A CN 108360011 A CN108360011 A CN 108360011A CN 201810317907 A CN201810317907 A CN 201810317907A CN 108360011 A CN108360011 A CN 108360011A
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- ammonia
- electrolytic
- hydrogen
- electrolytic cell
- coal liquefaction
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- Oil, Petroleum & Natural Gas (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to the system and methods that a kind of ammonia electrolytic hydrogen production is used for coal liquefaction, the system includes electrolyte supply system, electrolytic cell and coal liquefaction system, the electrolyte entrance of the outlet connection electrolytic cell of electrolyte supply system, the entrance of the cathode hydrogen outlet connection coal liquefaction system of electrolytic cell;It using conventional alkaline electrolysis pond, is electrolysed by ammonia and obtains high-purity hydrogen, and supply hydrogen to coal liquefaction system, hydrogenation liquefaction reaction occurs, promotes the clean utilization of coal resources;The present invention can reduce the energy consumption of electrolytic hydrogen production, reduce the cost of electrolytic hydrogen production, be conducive to the popularization of green harmless electrolytic hydrogen production mode;The ammonia in waste water can be also removed by electrolysis, realize the coupling of wastewater treatment and efficient electrolysis hydrogen manufacturing, and electrolysis hydrogen obtained is used for coal liquefaction, the clean and effective for promoting coal resources utilizes, and has higher environment protection significance and comprehensive benefit.
Description
Technical field
The present invention relates to hydrogen manufacturing and environmental technology field, more particularly to a kind of ammonia electrolytic hydrogen production for coal liquefaction system and
Method.
Background technology
In recent years, with the continuous reinforcement of people's environmental consciousness, the exploitation of new energy and the clean and effective profit of fossil energy
With having obtained more and more attention.The energy resource structure in China is the few oily deficency of more coals, within the following considerable time, coal
All will be the main energy sources in China.Coal liquefaction is a kind of important channel that Coal Clean efficiently utilizes, it is by coal in high temperature height
Under the conditions of pressure, by catalytic hydrogenation direct liquefaction synthesizing liquid HC fuel, and the atoms such as sulphur, nitrogen, oxygen are removed, to reduce ring
Border is polluted, and improves utilization ratio.
Hydrogen is the important source material of coal liquefaction.In various hydrogen production process, electrolytic hydrogen production wide, nothing with raw material sources
The advantages of pollution, clean and effective is the direction of the following hydrogen manufacturing development.However, due to electrolysis need consume electric energy, cost compared with
Height limits the popularization of electrolytic hydrogen production method.The current electrolysis hydrogen manufacturing mode of production only accounts for the 4% of whole hydrogen manufacturing modes.In order to push away
Wide green hydrogen manufacturing mode, needs the power consumption for reducing electrolytic hydrogen production.
The power consumption of cell reaction is related with the standard electrode EMF of cathode and anode reaction, and electrolysis water is reacted:
Cathode:
2H2O+2e-→H2+2OH-E °=- 0.83V vs SHE
Anode:
2OH-→1/2O2+H2O+2e-E °=0.40V vs SHE
Overall reaction:
2H2O+ electric energy → 2H2+O2E=1.23V
I.e. the minimum theoretical voltage of water electrolysis hydrogen production is 1.23V.Reduce theoretical voltage, it is necessary to reduce anodic oxidation reactions
Standard electrode EMF, this just needs to find a kind of suitable anode reactant.
Invention content
In order to overcome the defect of the above-mentioned prior art, the purpose of the present invention is to provide a kind of ammonia electrolytic hydrogen productions to be used for coal liquid
The system and method for change, the technical problem to be solved is that:By being electrolysed ammonia hydrogen making, and hydrogen is supplied to coal liquefaction system
System realizes that the clean and effective of the supply of low energy consumption green hydrogen and coal utilizes.
In order to achieve the above object, the technical scheme is that:
A kind of system that ammonia electrolytic hydrogen production is used for coal liquefaction, including electrolyte supply system 1, electrolytic cell 2 and coal liquefaction system
System 3;Wherein, the electrolyte entrance of the outlet connection electrolytic cell 2 of electrolyte supply system 1, the cathode hydrogen outlet of electrolytic cell 2 connect
Connect the entrance of coal liquefaction system 3.
The electrolyte supply system 1 includes stirred tank, ammonium hydroxide feeding device and KOH the charging dress being connected to stirred tank
It sets, is connected to the delivery pump and corresponding pipeline of stirred tank and ammonium hydroxide feeding device and KOH feeding devices.
The electrolytic cell 2 is conventional alkaline electrolytic cell, and cathode and anode catalyst material are Pt, Ru, Rh, Ir, Ni, Co,
One or more alloys in Fe, Zn, Ti and Ta metal.
The coal liquefaction system 3 includes catalyst reaction device and oil product collection device.
The system carries out the method that ammonia electrolytic hydrogen production is used for coal liquefaction, includes the following steps:
Step 1:The mixed electrolytic solution of ammonia and KOH is prepared in electrolyte supply system 1;
Step 2:Mixed electrolytic solution is passed through in electrolytic cell 2, is powered in electrolytic cell 2 and the following reaction of electrolysis occurs:
Cathode:
2H2O+2e-→H2+2OH-E °=- 0.83V vs SHE
Anode:
2OH-→1/2O2+H2O+2e-E °=0.40V vs SHE
Overall reaction:
2H2O+ electric energy → 2H2+O2E=1.23V
Hydrogen is generated in the cathode of electrolytic cell 2, the water of nitrogen and deamination is generated in anode;
Step 3:Hydrogenation liquefaction is carried out with coal slurry to react, generate naphtha, aviation fuel and diesel oil using the hydrogen in step 2.
In the step 1, ammonia derives from industrial and agricultural wastewater, and system plays the work of waste water ammonia-removal while producing hydrogen at this time
With.
In the step 2, mixed electrolytic solution is alkaline electrolyte, includes the KOH and 0.01-2mol/L of 0.2-2mol/L
Ammonia;Cell reaction carries out at normal temperatures.
In the step 2, the power supply of electrolytic cell 2 is wind-powered electricity generation, photovoltaic class renewable energy power generation;
In the step 2, in the hydrogen purity that the cathode of electrolytic cell 2 obtains 99.9% or more;In the anode of electrolytic cell
Nitrogen is obtained, is sold after collection;Anode obtains the water of low ammonia content, as industrial reuse water.
In the step 3, including prepared by coal slurry, hydrogenation liquefaction reaction, stabilized hydrogenation reacts and modification reaction.
Compared to the prior art compared with the present invention has following features:
(1) present invention utilizes ammonia Electrowinning hydrogen, theoretical voltage greatly to be dropped far below conventional water electrolysis hydrogen production
Low energy consumption;Ammonia is a kind of common industrial products, cheap, in addition also with the presence of a large amount of ammonia in industrial and agricultural wastewater,
Cheap raw material can be provided for electrolytic hydrogen production.Therefore, electrolysis ammonia hydrogen manufacturing is to reduce electrolytic hydrogen production energy consumption, reduce overall cost
Good selection;
(2) ammonia electrolytic hydrogen production can be generated electricity using clean energy resourcies such as water power, photovoltaic, wind-powered electricity generations and be carried out, and electrolysate only has hydrogen
And nitrogen, it cleans, is pollution-free;
(3) ammonia in electrolytic hydrogen production can further decrease system cost using the ammonia nitrogen in industrial and agricultural wastewater as source, and
Ammonia is become into nitrogen discharge by electrolysis, achievees the effect that wastewater treatment while producing hydrogen;
(4) electrolysis hydrogen obtained is used for coal liquefaction, the clean and effective for promoting coal resources utilizes.
Description of the drawings
Fig. 1 is the principle schematic in alkaline electrolysis pond.
Fig. 2 is the system schematic that ammonia electrolytic hydrogen production is used for coal liquefaction.
Specific implementation mode
The invention will now be described in detail with reference to the accompanying drawings.
Example 1:
As shown in Figure 1, the cathode of electrolytic cell 2 is Ni-Co-Fe alloy electrodes, anode is Ni-Rh alloy electrodes, alkaline electro
Solution liquid ingredient be:1mol/L KOH, 1mol/L NH3.Ammonia in alkaline electrolyte is supplemented by industrial ammonia.Such as Fig. 2 institutes
Show, the alkaline electrolyte being made into electrolyte supply system 1 is squeezed into electrolytic cell 2, occurs under the applied voltage of 0.8V
Cell reaction, the high-purity hydrogen that purity reaches 99.9% is generated in the cathode of electrolytic cell 2, and nitrogen is generated in the anode of electrolytic cell 2
With the water of low ammonia content.Enter coal liquefaction system 3 in the high-purity hydrogen that the cathode of electrolytic cell 2 generates, with coal slurry in high temperature and pressure
Lower generation hydrogenation catalyst reaction, generates naphtha and diesel oil, is collected respectively through product separation and collection device.
Claims (10)
1. the system that a kind of ammonia electrolytic hydrogen production is used for coal liquefaction, it is characterised in that:Including electrolyte supply system (1), electrolytic cell
(2) and coal liquefaction system (3);Wherein, the electrolyte entrance of the outlet connection electrolytic cell (2) of electrolyte supply system (1), electrolysis
The entrance of the cathode hydrogen outlet connection coal liquefaction system (3) in pond (2).
2. the system that a kind of ammonia electrolytic hydrogen production according to claim 1 is used for coal liquefaction, it is characterised in that:The electrolyte
Supply system (1) includes stirred tank, the ammonium hydroxide feeding device and KOH feeding devices being connected to stirred tank, is connected to stirred tank and ammonia
The delivery pump and corresponding pipeline of water feeding device and KOH feeding devices.
3. the system that a kind of ammonia electrolytic hydrogen production according to claim 1 is used for coal liquefaction, it is characterised in that:The electrolytic cell
(2) it is conventional alkaline electrolytic cell, cathode and anode catalyst material are Pt, Ru, Rh, Ir, Ni, Co, Fe, Zn, Ti and Ta metal
In one or more alloys.
4. the system that a kind of ammonia electrolytic hydrogen production according to claim 1 is used for coal liquefaction, it is characterised in that:The coal liquefaction
System (3) includes catalyst reaction device and oil product collection device.
5. system described in claim 1 carries out the method that ammonia electrolytic hydrogen production is used for coal liquefaction, which is characterized in that including walking as follows
Suddenly:
Step 1:The mixed electrolytic solution of ammonia and KOH is prepared in electrolyte supply system (1);
Step 2:Mixed electrolytic solution is passed through in electrolytic cell (2), is powered in electrolytic cell (2) and the following reaction of electrolysis occurs:
Cathode:
2H2O+2e-→H2+2OH-E °=- 0.83V vs SHE
Anode:
2OH-→1/2O2+H2O+2e-E °=0.40V vs SHE
Overall reaction:
2H2O+ electric energy → 2H2+O2E=1.23V
Hydrogen is generated in the cathode of electrolytic cell (2), the water of nitrogen and deamination is generated in anode;
Step 3:Hydrogenation liquefaction is carried out with coal slurry to react, generate naphtha, aviation fuel and diesel oil using the hydrogen in step 2.
6. method as claimed in claim 5, it is characterised in that:In the step 1, ammonia derives from industrial and agricultural wastewater, is at this time
System plays the role of waste water ammonia-removal while producing hydrogen.
7. method as claimed in claim 5, it is characterised in that:In the step 2, mixed electrolytic solution is alkaline electrolyte, packet
The ammonia of KOH and 0.01-2mol/L containing 0.2-2mol/L;Cell reaction carries out at normal temperatures.
8. method as claimed in claim 5, it is characterised in that:In the step 2, the power supply of electrolytic cell (2) is wind-powered electricity generation, photovoltaic
Class renewable energy power generation.
9. method as claimed in claim 5, it is characterised in that:In the step 2, in the hydrogen that the cathode of electrolytic cell (2) obtains
Gas purity is 99.9% or more;Nitrogen is obtained in the anode of electrolytic cell (2), is sold after collection;Anode obtains low ammonia content
Water, as industrial reuse water.
10. method as claimed in claim 5, it is characterised in that:In the step 3, including prepared by coal slurry, hydrogenation liquefaction is anti-
It answers, stabilized hydrogenation reaction and modification are reacted.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111617774A (en) * | 2020-06-10 | 2020-09-04 | 贵州大学 | Synthesis and application of quaternary platinum-iron-rhodium-ruthenium nano alloy with hierarchical structure |
CN115557633A (en) * | 2022-09-28 | 2023-01-03 | 西南石油大学 | Integrated system for wastewater treatment and electrolytic hydrogen production and operation method |
CN115627487A (en) * | 2022-10-31 | 2023-01-20 | 西南石油大学 | Solar power generation and water electrolysis combined hydrogen production and building environment dehumidification system |
KR20230045919A (en) * | 2021-09-29 | 2023-04-05 | 주식회사 에이이에스텍 | Fluid separator and Ammonia electrolysis system include the same |
WO2023054964A1 (en) * | 2021-09-29 | 2023-04-06 | 주식회사 에이이에스텍 | Ammonia electrolysis system and control method therefor |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104419945A (en) * | 2013-08-28 | 2015-03-18 | 中国科学院青岛生物能源与过程研究所 | Method and device for preparing hydrogen by electrolyzing ammonia |
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2018
- 2018-04-10 CN CN201810317907.9A patent/CN108360011A/en not_active Withdrawn
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104419945A (en) * | 2013-08-28 | 2015-03-18 | 中国科学院青岛生物能源与过程研究所 | Method and device for preparing hydrogen by electrolyzing ammonia |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111617774A (en) * | 2020-06-10 | 2020-09-04 | 贵州大学 | Synthesis and application of quaternary platinum-iron-rhodium-ruthenium nano alloy with hierarchical structure |
CN111617774B (en) * | 2020-06-10 | 2022-11-08 | 贵州大学 | Synthesis and application of quaternary platinum-iron-rhodium-ruthenium nano alloy with hierarchical structure |
KR20230045919A (en) * | 2021-09-29 | 2023-04-05 | 주식회사 에이이에스텍 | Fluid separator and Ammonia electrolysis system include the same |
WO2023054964A1 (en) * | 2021-09-29 | 2023-04-06 | 주식회사 에이이에스텍 | Ammonia electrolysis system and control method therefor |
KR102577573B1 (en) * | 2021-09-29 | 2023-09-12 | 주식회사 에이이에스텍 | Fluid separator and Ammonia electrolysis system include the same |
CN115557633A (en) * | 2022-09-28 | 2023-01-03 | 西南石油大学 | Integrated system for wastewater treatment and electrolytic hydrogen production and operation method |
CN115557633B (en) * | 2022-09-28 | 2023-05-05 | 西南石油大学 | Integrated system for wastewater treatment and electrolytic hydrogen production and operation method |
CN115627487A (en) * | 2022-10-31 | 2023-01-20 | 西南石油大学 | Solar power generation and water electrolysis combined hydrogen production and building environment dehumidification system |
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Application publication date: 20180803 |