CN110467153A - A kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen reduction hydrogen production process - Google Patents
A kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen reduction hydrogen production process Download PDFInfo
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- CN110467153A CN110467153A CN201910768023.XA CN201910768023A CN110467153A CN 110467153 A CN110467153 A CN 110467153A CN 201910768023 A CN201910768023 A CN 201910768023A CN 110467153 A CN110467153 A CN 110467153A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/02—Preparation of nitrogen
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- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/068—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents the hydrogen being generated from the water as a result of a cyclus of reactions, not covered by groups C01B3/063 or C01B3/105
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of iodine selenium thermochemical cycles nitrogen to restore hydrogen production process, belongs to Hydrogen Technology field.First using water as raw material, selenium and iodine is added, reacts under normal pressure, obtains selenous acid solution and hydroiodic acid, rectifying concentration is carried out to hydroiodic acid, hydroiodic acid after rectifying concentration is decomposed, the hydrogen decomposed is recycled as output of products, iodine, reducing agent hydrazine hydrate or hydrazine hydrate or ammonia (ammonium hydroxide) are added in obtained selenous acid solution, selenium, nitrogen and vapor are obtained, nitrogen is used as byproduct to export after drying, and selenium is used as feedstock circulation.Maximum temperature needed for the reaction process of the method for the present invention is 400-500 DEG C, avoids the problem of big regular hydrogen manufacturing production can not be carried out because reaction temperature is excessively high.Reactant iodine and selenium in the method for the present invention, can recycle, therefore greatly reduce the production cost of hydrogen manufacturing.This method can be very good to couple with newest clean energy resource high temperature gas cooled reactor, and thermal energy, electric energy and the mechanical energy of high temperature gas cooled reactor can be utilized by iodine selenium thermochemical cycle for hydrogen production process.
Description
Technical field
The present invention relates to a kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen to restore hydrogen production process, belongs to Hydrogen Technology
Field.
Background technique
Hydrogen Energy is a kind of ideal cleaning secondary energy sources, and widely distributed, burning does not generate pollution, and relative to electricity
Power, hydrogen is more convenient for storing transport, and can be paid more and more attention directly as fuel by the energy system of core of Hydrogen Energy.Heat
Chemical cycle hydrogen production by water decomposition is one of most promising method.The method of thermochemical cycle for hydrogen production common at present is that sulphur iodine follows
Ring hydrogen manufacturing, if Chinese patent application (application publication number CN104817057) discloses a kind of method of thermochemical cycle for hydrogen production,
This method includes 3 chemical reactions, as follows:
Bunsen reaction:
SO2+I2+2H2O→2HI+H2SO4(T=290-390K)
Sulfuric acid decomposition reaction:
H2SO4→H2O+SO2+0.5O2(T=970-1270K)
Hydroiodic acid decomposition reaction:
2HI→H2+I2(T=570-770K)
Theoretically, water can be with hydrogen manufacturing by thermal dissociation, but reaction needs 4000 DEG C or more of high temperature, and sulphur iodine recycles hydrogen manufacturing
Method is that the decomposition reaction of water is divided into several steps, can not only reduce reaction temperature in this way, but can to avoid hydrogen-oxygen separation problem, and
And sulfur dioxide used in circulation and iodine can be recycled.The shortcomings that sulphur iodine circulation silicol process is that the decomposition of sulfuric acid is anti-
Higher temperature should be still needed, and also in laboratory scale, the heat dissipation that consumes energy is very high.If extensive hydrogen manufacturing, needs energy
The stabilization heat source of offer high temperature, and such eligible high-temperature stable heavy construction heat source for being capable of providing 970K temperature or more
There is not yet.
Summary of the invention
The purpose of the present invention is to propose to a kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen to restore hydrogen production process, to
Some heat chemistry sulphur iodine circulation process for making hydrogen improves, with using be capable of providing stabilization heat source-high temperature gas cooled reactor of high temperature into
Row coupling, realizes extensive hydrogen manufacturing.
High temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen proposed by the present invention restores hydrogen production process, comprising the following steps:
(1) using water as raw material, selenium and iodine is added, reacts under normal pressure, the molar ratio of water, selenium and iodine are as follows: water: selenium: iodine=
1:(0.3-2): (0.5-4), reaction temperature are 15 DEG C -80 DEG C, reaction time 30-120min, and reaction obtains selenous acid solution
And hydroiodic acid, reaction equation are as follows:
3H2O+Se+2I2→H2SeO3+4HI
Using Liquid liquid Separation method, selenous acid solution and hydroiodic acid are subjected to Liquid liquid Separation, obtain selenous acid solution and hydrogen
Acid iodide；
(2) rectifying is carried out to the hydroiodic acid that step (1) obtains, rectifying column feeding temperature is bubble point temperature, and tower pressure interior force is
1.1-1.5MPa, reaction time 10-50min；
(3) hydroiodic acid obtained to step (2) decomposes, and decomposition tower pressure interior force is 1.1-1.5MPa, and reaction temperature is
400 DEG C -700 DEG C, reaction time 30-120min, product is hydrogen and iodine, and for hydrogen as output of products, iodine returns to step (1)
Middle recycling, chemical equation are as follows:
2HI→H2+I2
(4) reducing agent is added in the selenous acid solution that step (1) obtains, molar ratio is added are as follows: selenous acid: reducing agent=
1:(1-10), at 100 DEG C -400 DEG C, reaction time 30-120min obtains selenium, nitrogen and vapor, and nitrogen is made after drying
For byproduct output, selenium is returned in step (1) and is used as feedstock circulation, and reaction equation is as follows:
H2SeO3+N2H4·H2O→Se+N2+4H2O
H2SeO3+4(NH2OH·H2O)→Se+2N2+11H2O
In above-mentioned nitrogen reduction hydrogen production process, the reducing agent is hydrazine hydrate, hydrazine hydrate or ammonia (or ammonium hydroxide).Work as institute
When the reducing agent stated is hydrazine hydrate, the molar ratio of selenous acid and hydrazine hydrate are as follows: selenous acid: hydrazine hydrate=1:(1-3).When
When the reducing agent is hydrazine hydrate, selenous acid and hydrazine hydrate molar ratio are as follows: selenous acid: hydrazine hydrate=1:(4-6).When described
When reducing agent is ammonia (or ammonium hydroxide), selenous acid and ammonia (or ammonium hydroxide) molar ratio are as follows: selenous acid: ammonia (or ammonium hydroxide)=1:
(2-5)。
In above-mentioned nitrogen reduction hydrogen production process, the step (4) are as follows: selenous acid solution is decomposed, reaction temperature is
100 DEG C -200 DEG C, decomposition obtains product selenium dioxide and vapor, and reducing agent hydrazine hydrate, dioxy are added in selenium dioxide
Change selenium and hydrazine hydrate molar ratio are as follows: selenium dioxide: hydrazine hydrate=1:(1-3), the reaction time are as follows: 30-120min, reaction is extremely
No longer generating gas is fully reacting, generates selenium and steam-laden nitrogen, selenium returns in step (1) to be made as feedstock circulation
With nitrogen is used as byproduct to export after drying, and reaction equation is as follows:
H2SeO3→SeO2+H2O
SeO2+N2H4·H2O→Se+N2+3H2O。
In above-mentioned nitrogen reduction hydrogen production process, the step (4) can be with are as follows: decomposes, reacts to selenous acid solution
Temperature is 100 DEG C -200 DEG C, and decomposition obtains product selenium dioxide and vapor, and reducing agent hydrazine hydrate is added in selenium dioxide,
Selenium dioxide and hydrazine hydrate molar ratio are as follows: selenium dioxide: hydrazine hydrate=1:(4-6), the reaction time are as follows: 30-120min, reaction is extremely
No longer generating gas is fully reacting, generates selenium and steam-laden nitrogen, selenium returns in step (1) to be made as feedstock circulation
With nitrogen is used as byproduct to export after drying, and reaction equation is as follows:
H2SeO3→SeO2+H2O
SeO2+4(NH2OH·H2O)→Se+2N2+10H2O。
In above-mentioned nitrogen reduction hydrogen production process, the step (4) can be with are as follows: selenous acid obtained in step (1) is molten
Liquid is decomposed, and reaction temperature is 100 DEG C -200 DEG C, and decomposition obtains product selenium dioxide and vapor, in obtained titanium dioxide
Reducing agent ammonia (or ammonium hydroxide) is added in selenium, selenium dioxide and ammonia (or ammonium hydroxide) molar ratio are as follows: selenium dioxide and ammonia (or ammonia
Water)=1:(4-6), reaction time 30-120min, reaction is fully reacting to gas is no longer generated, and generates selenium and aqueous steaming
The nitrogen of gas, selenium will be returned in step (1) and uses as feedstock circulation, and nitrogen is used as byproduct to export after drying, reaction side
Formula is as follows:
H2SeO3→SeO2+H2O
3SeO2+4NH3→3Se+2N2+6H2O
In above-mentioned iodine selenium thermochemical cycles nitrogen reduction hydrogen production process, the reaction temperature in step (1) is 20 DEG C -30 DEG C.
In above-mentioned iodine selenium thermochemical cycles nitrogen reduction hydrogen production process, reaction temperature is 400 DEG C -500 DEG C in step (3).
In above-mentioned iodine selenium thermochemical cycles nitrogen reduction hydrogen production process, reaction temperature is 100 DEG C -200 DEG C in step (4).
High temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen proposed by the present invention restores hydrogen production process, and features and advantages are such as
Under:
1, high temperature gas cooled reactor of the invention coupling iodine selenium thermochemical cycles nitrogen restores hydrogen production process, highest needed for reaction process
Temperature is 400 DEG C -500 DEG C, avoids the problem of big regular hydrogen manufacturing production can not be carried out because reaction temperature is excessively high.
2, nitrogen of the invention restores hydrogen production process, and reactant iodine and selenium therein can recycle, therefore substantially reduce
The production cost of hydrogen manufacturing.
3, high temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen of the invention restores hydrogen production process, using high temperature gas cooled reactor with
Each chemical industry equipment of iodine selenium thermochemical cycles system couples, due to reactant selenium, selenium dioxide, reducing agent and intermediate product Asia selenium
Acid and hydroiodic acid belong to strong corrosive or severe toxicity, and therefore, equipment, pipeline and pump etc. need corrosion-resistant and zero leakage, make in process
Zero leakage is realized with torque Magnetic drive.
4, high temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen of the invention restores hydrogen production process, is used for and high temperature gas cooled reactor
Coupling, and high temperature gas cooled reactor can provide the energy of three kinds of forms, i.e. thermal energy, electric energy and mechanical energy, it can be by iodine selenium heat chemistry
Circulation hydrogen production process is utilized.The thermal energy that high temperature gas cooled reactor generates can be transmitted with cascade utilization, heat by Intermediate Heat Exchanger, and
It is 700 DEG C, 500 DEG C, 300 DEG C and 100 DEG C that temperature gradient, which is arranged, makes full use of thermal energy, the utilization of thermal energy in this way
Rate can reach 99%.In addition, high temperature gas cooled reactor itself generates electricity, the electric energy of generation be can also be used in subsequent iodine selenium thermochemical cycles,
It is utilized by electrical equipments such as motors, utilization rate can also reach 30-50%.In addition, a large amount of steam that high temperature gas cooled reactor generates
Also it can provide mechanical energy, directly coupled with the steam turbine in iodine selenium thermochemical cycles system, utilization efficiency is up to 90%.
5, high temperature gas cooled reactor of the invention coupling iodine selenium thermochemical cycles nitrogen restores hydrogen production process, is not limited to use High Temperature Gas
Cold dome is coupled, and also be can be used other high temperature heat sources to restore hydrogen production process with iodine selenium thermochemical cycles nitrogen and is coupled.
Specific embodiment
High temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen proposed by the present invention restores hydrogen production process, comprising the following steps:
(1) using water as raw material, selenium and iodine is added, reacts under normal pressure, the molar ratio of water, selenium and iodine are as follows: water: selenium: iodine=
1:(0.3-2): (0.5-4), reaction temperature are 15 DEG C -80 DEG C, reaction time 30-120min, and the mark of fully reacting is not
Gas is generated again, and reaction obtains selenous acid solution and hydroiodic acid, and reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
The hydroiodic acid of above-mentioned generation and selenous acid are obviously layered because of density difference, and hydroiodic acid is in upper layer, selenous acid solution
In lower layer.Using Liquid liquid Separation method, selenous acid solution and hydroiodic acid are subjected to Liquid liquid Separation, obtain selenous acid solution and hydrogen iodine
Acid.
It (2) include following components in the hydroiodic acid obtained to step (1): I2, HI and H2O, mixed ternary solution are denoted as
HIx solution.HIx solution, which enters in HI rectifying decomposition unit, carries out rectifying, and rectifying column feeding temperature is bubble point temperature, tower pressure interior force
For 1.1-1.5MPa, reaction time 10-50min.
(3) hydroiodic acid obtained to step (2) decomposes, and decomposition tower pressure interior force is 1.1-1.5MPa, and reaction temperature is
400 DEG C -700 DEG C, reaction time 30-120min, product H2And I2, as output of products, iodine returns in step (1) hydrogen
It is recycled, chemical equation is as follows:
2HI→H2+I2
Hot environment in step, is provided by high temperature gas cooled reactor, and the high temperature hot steam of high temperature gas cooled reactor is passed by heat exchanger
To hydroiodic acid decomposition tower.
(4) reducing agent is added in the selenous acid solution that step (1) obtains, molar ratio is added are as follows: selenous acid: reducing agent=
1:(1-10), at 100 DEG C -200 DEG C, reaction time 30-120min, reaction is obtained to gas is not regenerated as reaction completion
Selenium, nitrogen and vapor, nitrogen are used as byproduct to export after drying, and selenium is returned in step (1) and used as feedstock circulation.Instead
Answer principle equation as follows:
H2SeO3+N2H4·H2O→Se+N2+4H2O
H2SeO3+4(NH2OH·H2O)→Se+2N2+11H2O
Since step (1), step (2), step (3), step (4) have extremely toxic substance selenium, selenous acid, selenium dioxide, reduction
The participation of the substances such as agent and strong corrosive material hydroiodic acid, therefore, equipment, pipeline and pump etc. need corrosion-resistant and zero leakage, stream
In journey zero leakage will be realized using torque Magnetic drive.
In above-mentioned nitrogen reduction hydrogen production process, the reducing agent is hydrazine hydrate, hydrazine hydrate or ammonia (or ammonium hydroxide).Work as institute
When the reducing agent stated is hydrazine hydrate, the molar ratio of selenous acid and hydrazine hydrate are as follows: selenous acid: hydrazine hydrate=1:(1-3).When
When the reducing agent is hydrazine hydrate, selenous acid and hydrazine hydrate molar ratio are as follows: selenous acid: hydrazine hydrate=1:(4-6).When described
When reducing agent is ammonia (or ammonium hydroxide), the molar ratio of selenous acid and ammonia or ammonium hydroxide are as follows: selenous acid: ammonia or ammonium hydroxide=1:(2-
5)。
In above-mentioned nitrogen reduction hydrogen production process, the step (4) are as follows: selenous acid solution is decomposed, reaction temperature is
100 DEG C -200 DEG C, decomposition obtains product selenium dioxide and vapor, and reducing agent hydrazine hydrate, dioxy are added in selenium dioxide
Change selenium and hydrazine hydrate molar ratio are as follows: selenium dioxide: hydrazine hydrate=1:(1-3), the reaction time are as follows: 30-120min, reaction is extremely
No longer generating gas is fully reacting, generates selenium and steam-laden nitrogen, selenium returns in step (1) to be made as feedstock circulation
With nitrogen is used as byproduct to export after drying, and reaction equation is as follows:
H2SeO3→SeO2+H2O
SeO2+N2H4·H2O→Se+N2+3H2O。
In above-mentioned nitrogen reduction hydrogen production process, the step (4) can be with are as follows: decomposes, reacts to selenous acid solution
Temperature is 100 DEG C -200 DEG C, and decomposition obtains product selenium dioxide and vapor, and reducing agent hydrazine hydrate is added in selenium dioxide,
Selenium dioxide and hydrazine hydrate molar ratio are as follows: selenium dioxide: hydrazine hydrate=1:(4-6), the reaction time are as follows: 30-120min, reaction is extremely
No longer generating gas is fully reacting, generates selenium and steam-laden nitrogen, selenium returns in step (1) to be made as feedstock circulation
With nitrogen is used as byproduct to export after drying, and reaction equation is as follows:
H2SeO3→SeO2+H2O
SeO2+4(NH2OH·H2O)→Se+2N2+10H2O。
In above-mentioned nitrogen reduction hydrogen production process, the step (4) can be with are as follows: selenous acid obtained in step (1) is molten
Liquid is decomposed, and reaction temperature is 100 DEG C -200 DEG C, and decomposition obtains product selenium dioxide and vapor, in obtained titanium dioxide
Reducing agent ammonia (or ammonium hydroxide) is added in selenium, selenium dioxide and ammonia (or ammonium hydroxide) molar ratio are as follows: selenium dioxide: ammonia (or ammonia
Water)=1:(4-6), reaction time 30-120min, reaction is fully reacting to gas is no longer generated, and generates selenium and aqueous steaming
The nitrogen of gas, selenium will be returned in step (1) and uses as feedstock circulation, and nitrogen is used as byproduct to export after drying, reaction side
Formula is as follows:
H2SeO3→SeO2+H2O
3SeO2+4NH3→3Se+2N2+6H2O
In above-mentioned iodine selenium thermochemical cycles nitrogen reduction hydrogen production process, the reaction temperature in step (1) is 20 DEG C -30 DEG C.
In above-mentioned iodine selenium thermochemical cycles nitrogen reduction hydrogen production process, reaction temperature is 400 DEG C -500 DEG C in step (3).
In above-mentioned iodine selenium thermochemical cycles nitrogen reduction hydrogen production process, reaction temperature is 100 DEG C -200 DEG C in step (4).
The embodiment of the method for the present invention introduced below:
Embodiment one
(1) using water as raw material, selenium and iodine is added, reacts under normal pressure, the molar ratio of water, selenium and iodine are as follows: water: selenium: iodine=
1:0.4:1, reaction temperature are 25 DEG C, reaction time 60min, and the mark of fully reacting is no longer to generate gas, and reaction obtains
Selenous acid solution and hydroiodic acid, reaction equation are as follows:
3H2O+Se+2I2→H2SeO3+4HI
The hydroiodic acid of above-mentioned generation and selenous acid are obviously layered because of density difference, and hydroiodic acid is in upper layer, selenous acid solution
In lower layer.Using Liquid liquid Separation method, selenous acid solution and hydroiodic acid are subjected to Liquid liquid Separation, obtain selenous acid solution and hydrogen iodine
Acid；
It (2) include following components in the hydroiodic acid obtained to step (1): I2, HI and H2O, mixed ternary solution are denoted as
HIx solution.HIx solution, which enters in HI rectifying decomposition unit, carries out rectifying, and rectifying column feeding temperature is bubble point temperature, tower pressure interior force
For 1.17MPa, reaction time 30min.
(3) hydroiodic acid after step (2) rectifying is decomposed, decomposition tower pressure interior force is 1.17MPa, and reaction temperature is
480 DEG C, reaction time 60min, product H2And I2, as output of products, iodine is returned in step (1) and is recycled hydrogen；This
The chemical principle of process such as chemical equation is as follows:
2HI→H2+I2
Hot environment in this step, is provided by high temperature gas cooled reactor, and the high-temperature steam of high temperature gas cooled reactor is passed by heat exchanger
To hydroiodic acid decomposition tower.
(4) reducing agent hydrazine hydrate is added in the selenous acid solution that step (1) obtains, molar ratio is added are as follows: selenous acid:
Reducing agent=1:1, at 120 DEG C, reaction time 120min, reaction obtains selenium, nitrogen to gas is not regenerated as reaction completion
And vapor, nitrogen are used as byproduct to export after drying, selenium is returned in step (1) and is used as feedstock circulation.Reaction principle
Equation is as follows.
H2SeO3+N2H4·H2O→Se+N2+4H2O
Since step (1), step (2), step (3), step (4) have extremely toxic substance selenium, selenous acid, selenium dioxide, reduction
The participation of the substances such as agent and strong corrosive material hydroiodic acid, therefore, equipment, pipeline and pump etc. need corrosion-resistant and zero leakage, stream
In journey zero leakage will be realized using torque Magnetic drive.
Embodiment two
(1) using water as raw material, selenium and iodine is added, reacts under normal pressure, the molar ratio of water, selenium and iodine are as follows: water: selenium: iodine=
1:0.5:1.2, reaction temperature are 28 DEG C, reaction time 50min, and the mark of fully reacting is no longer to generate gas, are reacted
To selenous acid solution and hydroiodic acid, reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
The hydroiodic acid of above-mentioned generation and selenous acid are obviously layered because of density difference, and hydroiodic acid is in upper layer, selenous acid solution
In lower layer.Using Liquid liquid Separation method, selenous acid solution and hydroiodic acid are subjected to Liquid liquid Separation, obtain selenous acid solution and hydrogen iodine
Acid；
It (2) include following components in the hydroiodic acid obtained to step (1): I2, HI and H2O, mixed ternary solution are denoted as
HIx solution.HIx solution, which enters in HI rectifying decomposition unit, carries out rectifying, and rectifying column feeding temperature is bubble point temperature, tower pressure interior force
For 1.2MPa, reaction time 23min.
(3) hydroiodic acid after step (2) rectifying is decomposed, decomposition tower pressure interior force is 1.2MPa, reaction temperature 450
DEG C, reaction time 55min, product H2And I2, as output of products, iodine is returned in step (1) and is recycled hydrogen；This mistake
The chemical principle of journey such as chemical equation is as follows:
2HI→H2+I2
Hot environment in this step, is provided by high temperature gas cooled reactor, and the high-temperature steam of high temperature gas cooled reactor is passed by heat exchanger
To hydroiodic acid decomposition tower.
(4) reducing agent hydrazine hydrate is added in the selenous acid solution that step (1) obtains, molar ratio is added are as follows: selenous acid: also
Former agent=1:1.3, at 150 DEG C, reaction time 110min, reaction obtains selenium, nitrogen to gas is not regenerated as reaction completion
And vapor, nitrogen are used as byproduct to export after drying, selenium is returned in step (1) and is used as feedstock circulation.Reaction principle
Equation is as follows:
H2SeO3+N2H4·H2O→Se+N2+4H2O
Since step (1), step (2), step (3), step (4) have extremely toxic substance selenium, selenous acid, selenium dioxide, reduction
The participation of the substances such as agent and strong corrosive material hydroiodic acid, therefore, equipment, pipeline and pump etc. need corrosion-resistant and zero leakage, stream
In journey zero leakage will be realized using torque Magnetic drive.
Embodiment three
(1) using water as raw material, selenium and iodine is added, reacts under normal pressure, the molar ratio of water, selenium and iodine are as follows: water: selenium: iodine=
1:1:2, reaction temperature are 28 DEG C, reaction time 48min, and the mark of fully reacting is no longer to generate gas, and reaction obtains Asia
Selenic acid solution and hydroiodic acid, reaction equation are as follows:
3H2O+Se+2I2→H2SeO3+4HI
The hydroiodic acid of above-mentioned generation and selenous acid are obviously layered because of density difference, and hydroiodic acid is in upper layer, selenous acid solution
In lower layer.Using Liquid liquid Separation method, selenous acid solution and hydroiodic acid are subjected to Liquid liquid Separation, obtain selenous acid solution and hydrogen iodine
Acid；
It (2) include following components in the hydroiodic acid obtained to step (1): I2, HI and H2O, mixed ternary solution are denoted as
HIx solution.HIx solution, which enters in HI rectifying decomposition unit, carries out rectifying, and rectifying column feeding temperature is bubble point temperature, tower pressure interior force
For 1.3MPa, reaction time 20min.
(3) hydroiodic acid after step (2) rectifying is decomposed, decomposition tower pressure interior force is 1.3MPa, reaction temperature 450
DEG C, reaction time 57min, product H2And I2, as output of products, iodine is returned in step (1) and is recycled hydrogen；This mistake
The chemical principle of journey such as chemical equation is as follows:
2HI→H2+I2
Hot environment in this step, is provided by high temperature gas cooled reactor, and the high-temperature steam of high temperature gas cooled reactor is passed by heat exchanger
To hydroiodic acid decomposition tower.
(4) selenous acid solution to be decomposed, reaction temperature is 110 DEG C, and decomposition obtains product selenium dioxide and vapor,
Reducing agent hydrazine hydrate, selenium dioxide and hydrazine hydrate molar ratio are added in selenium dioxide are as follows: selenium dioxide: hydrazine hydrate=
1:1, reaction time are as follows: 120min, reaction are fully reacting to gas is no longer generated, and generate selenium and steam-laden nitrogen, selenium
It returns in step (1) and is used as feedstock circulation, nitrogen is used as byproduct to export after drying.The following institute of reaction principle equation
Show:
H2SeO3→SeO2+H2O
SeO2+N2H4·H2O→Se+N2+3H2O。
Since step (1), step (2), step (3), step (4) have extremely toxic substance selenium, selenous acid, selenium dioxide, reduction
The participation of the substances such as agent and strong corrosive material hydroiodic acid, therefore, equipment, pipeline and pump etc. need corrosion-resistant and zero leakage, stream
In journey zero leakage will be realized using torque Magnetic drive.
Example IV
(1) using water as raw material, selenium and iodine is added, reacts under normal pressure, the molar ratio of water, selenium and iodine are as follows: water: selenium: iodine=
1:1.3:2.7, reaction temperature are 28 DEG C, reaction time 40min, and the mark of fully reacting is no longer to generate gas, are reacted
To selenous acid solution and hydroiodic acid, reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
The hydroiodic acid of above-mentioned generation and selenous acid are obviously layered because of density difference, and hydroiodic acid is in upper layer, selenous acid solution
In lower layer.Using Liquid liquid Separation method, selenous acid solution and hydroiodic acid are subjected to Liquid liquid Separation, obtain selenous acid solution and hydrogen iodine
Acid；
It (2) include following components in the hydroiodic acid obtained to step (1): I2, HI and H2O, mixed ternary solution are denoted as
HIx solution.HIx solution, which enters in HI rectifying decomposition unit, carries out rectifying, and rectifying column feeding temperature is bubble point temperature, tower pressure interior force
For 1.17MPa, reaction time 30min.；
(3) hydroiodic acid after step (2) rectifying is decomposed, decomposition tower pressure interior force is 1.17MPa, and reaction temperature is
450 DEG C, reaction time 65min, product H2And I2, as output of products, iodine is returned in step (1) and is recycled hydrogen；This
The chemical principle of process such as chemical equation is as follows:
2HI→H2+I2
Hot environment in this step, is provided by high temperature gas cooled reactor, and the high-temperature steam of high temperature gas cooled reactor is passed by heat exchanger
To hydroiodic acid decomposition tower.
(4) selenous acid solution to be decomposed, reaction temperature is 150 DEG C, and decomposition obtains product selenium dioxide and vapor,
Reducing agent hydrazine hydrate, selenium dioxide and hydrazine hydrate molar ratio are added in selenium dioxide are as follows: selenium dioxide: hydrazine hydrate=
1:4.5, reaction time are as follows: 110min, reaction are fully reacting to gas is no longer generated, and generate selenium and steam-laden nitrogen,
Selenium is returned in step (1) and is used as feedstock circulation, and nitrogen is used as byproduct to export after drying.Reaction principle equation is as follows
It is shown:
H2SeO3→SeO2+H2O
SeO2+4(NH2OH·H2O)→Se+2N2+10H2O
Since step (1), step (2), step (3), step (4) have extremely toxic substance selenium, selenous acid, selenium dioxide, reduction
The participation of the substances such as agent and strong corrosive material hydroiodic acid, therefore, equipment, pipeline and pump etc. need corrosion-resistant and zero leakage, stream
In journey zero leakage will be realized using torque Magnetic drive.
Embodiment five
(1) using water as raw material, selenium and iodine is added, reacts under normal pressure, the molar ratio of water, selenium and iodine are as follows: water: selenium: iodine=
1:1.6:3.7, reaction temperature are 25 DEG C, reaction time 60min, and the mark of fully reacting is no longer to generate gas, are reacted
To selenous acid solution and hydroiodic acid, reaction equation is as follows:
3H2O+Se+2I2→H2SeO3+4HI
The hydroiodic acid of above-mentioned generation and selenous acid are obviously layered because of density difference, and hydroiodic acid is in upper layer, selenous acid solution
In lower layer.Using Liquid liquid Separation method, selenous acid solution and hydroiodic acid are subjected to Liquid liquid Separation, obtain selenous acid solution and hydrogen iodine
Acid；
It (2) include following components in the hydroiodic acid obtained to step (1): I2, HI and H2O, mixed ternary solution are denoted as
HIx solution.HIx solution, which enters in HI rectifying decomposition unit, carries out rectifying, and rectifying column feeding temperature is bubble point temperature, tower pressure interior force
For 1.4MPa, reaction time 15min.
(3) hydroiodic acid after step (2) rectifying is decomposed, decomposition tower pressure interior force is 1.4MPa, reaction temperature 410
DEG C, reaction time 54min, product H2And I2, as output of products, iodine is returned in step (1) and is recycled hydrogen；This mistake
The chemical principle of journey such as chemical equation is as follows:
2HI→H2+I2
Hot environment in this step, is provided by high temperature gas cooled reactor, and the high-temperature steam of high temperature gas cooled reactor is passed by heat exchanger
To hydroiodic acid decomposition tower.
(4) selenous acid solution to be decomposed, reaction temperature is 180 DEG C, and decomposition obtains product selenium dioxide and vapor,
Reducing agent hydrazine hydrate, selenium dioxide and hydrazine hydrate molar ratio are added in selenium dioxide are as follows: selenium dioxide: hydrazine hydrate=
1:5, reaction time are as follows: 100min, reaction are fully reacting to gas is no longer generated, and generate selenium and steam-laden nitrogen, selenium
It will be returned in step (1) and used as feedstock circulation, nitrogen is used as byproduct to export after drying.Reaction principle equation is as follows
It is shown:
H2SeO3→SeO2+H2O
3SeO2+4NH3→3Se+2N2+6H2O。
Since step (1), step (2), step (3), step (4) have extremely toxic substance selenium, selenous acid, selenium dioxide, reduction
The participation of the substances such as agent and strong corrosive material hydroiodic acid, therefore, equipment, pipeline and pump etc. need corrosion-resistant and zero leakage, stream
In journey zero leakage will be realized using torque Magnetic drive.
Claims (11)
1. a kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles nitrogen restores hydrogen production process, it is characterised in that this method includes following
Step:
(1) using water as raw material, selenium and iodine is added, reacts under normal pressure, the molar ratio of water, selenium and iodine are as follows: water: selenium: iodine=1:
(0.3-2): (0.5-4), reaction temperature be 15 DEG C -80 DEG C, reaction time 30-120min, reaction obtain selenous acid solution and
Hydroiodic acid, reaction equation are as follows:
3H2O+Se+2I2→H2SeO3+4HI
Using Liquid liquid Separation method, selenous acid solution and hydroiodic acid are subjected to Liquid liquid Separation, obtain selenous acid solution and hydroiodic acid；
(2) rectifying is carried out to the hydroiodic acid that step (1) obtains, rectifying column feeding temperature is bubble point temperature, tower pressure interior force 1.1-
1.5MPa, reaction time 10-50min；
(3) hydroiodic acid obtained to step (2) decomposes, and decomposition tower pressure interior force is 1.1-1.5MPa, reaction temperature 400
DEG C -700 DEG C, reaction time 30-120min, product H2And I2, for hydrogen as output of products, iodine returns to circulation in step (1)
It uses, chemical equation is as follows:
2HI→H2+I2
(4) reducing agent is added in the selenous acid solution that step (1) obtains, molar ratio is added are as follows: selenous acid: reducing agent=1:
(1-10), at 100 DEG C -400 DEG C, reaction time 30-120min obtains selenium, nitrogen and vapor, nitrogen conduct after drying
Byproduct output, selenium are returned in step (1) and are used as feedstock circulation, and reaction equation is as follows:
H2SeO3+N2H4·H2O→Se+N2+4H2O
H2SeO3+4(NH2OH·H2O)→Se+2N2+11H2O
2. iodine selenium thermochemical cycles nitrogen as described in claim 1 restores hydrogen production process, it is characterised in that the reducing agent is
Hydrazine hydrate or hydrazine hydrate or ammonia (ammonium hydroxide).
3. iodine selenium thermochemical cycles nitrogen as claimed in claim 2 restores hydrogen production process, it is characterised in that the reducing agent is
When hydrazine hydrate, the molar ratio of selenous acid and hydrazine hydrate are as follows: selenous acid: hydrazine hydrate=1:(1-3).
4. iodine selenium thermochemical cycles nitrogen as claimed in claim 2 restores hydrogen production process, it is characterised in that the reducing agent is
When hydrazine hydrate, selenous acid and hydrazine hydrate molar ratio are as follows: selenous acid: hydrazine hydrate=1:(4-6).
5. iodine selenium thermochemical cycles nitrogen as claimed in claim 2 restores hydrogen production process, it is characterised in that the reducing agent is
When ammonia or ammonium hydroxide, the molar ratio of selenous acid and ammonia or ammonium hydroxide are as follows: selenous acid: ammonia or ammonium hydroxide=1:(2-5).
6. iodine selenium thermochemical cycles nitrogen as described in claim 1 restores hydrogen production process, it is characterised in that the step (4)
Are as follows: selenous acid solution is decomposed, reaction temperature is 100 DEG C -200 DEG C, and decomposition obtains product selenium dioxide and vapor, In
Reducing agent hydrazine hydrate, selenium dioxide and hydrazine hydrate molar ratio are added in selenium dioxide are as follows: selenium dioxide: hydrazine hydrate=1:
(1-3), reaction time are as follows: 30-120min generates selenium and steam-laden nitrogen, and selenium returns in step (1) as feedstock circulation
It uses, nitrogen is used as byproduct to export after drying, and reaction equation is as follows:
H2SeO3→SeO2+H2O
SeO2+N2H4·H2O→Se+N2+3H2O。
7. iodine selenium thermochemical cycles nitrogen as described in claim 1 restores hydrogen production process, it is characterised in that the step (4)
Are as follows: selenous acid solution is decomposed, reaction temperature is 100 DEG C -200 DEG C, and decomposition obtains product selenium dioxide and vapor, In
Reducing agent hydrazine hydrate, selenium dioxide and hydrazine hydrate molar ratio are added in selenium dioxide are as follows: selenium dioxide: hydrazine hydrate=1:(4-6),
Reaction time are as follows: 30-120min, reaction are fully reacting to gas is no longer generated, and generate selenium and steam-laden nitrogen, selenium returns
It is used in step (1) as feedstock circulation, nitrogen is used as byproduct to export after drying, and reaction equation is as follows:
H2SeO3→SeO2+H2O
SeO2+4(NH2OH·H2O)→Se+2N2+10H2O。
8. iodine selenium thermochemical cycles nitrogen as described in claim 1 restores hydrogen production process, it is characterised in that the step (4)
Are as follows: selenous acid solution obtained in step (1) is decomposed, reaction temperature is 100 DEG C -200 DEG C, and decomposition obtains product dioxy
Change selenium and vapor, be added reducing agent ammonia or ammonium hydroxide in obtained selenium dioxide, selenium dioxide and ammonia or ammonium hydroxide rub
That ratio are as follows: selenium dioxide and ammonia or ammonium hydroxide=1:(4-6), reaction time 30-120min generates selenium and steam-laden nitrogen
Gas, selenium are returned in step (1) and are used as feedstock circulation, and nitrogen is used as byproduct to export after drying, and reaction equation is as follows:
H2SeO3→SeO2+H2O
3SeO2+4NH3→3Se+2N2+6H2O
9. iodine selenium thermochemical cycles nitrogen as described in claim 1 restores hydrogen production process, it is characterised in that in the step (1)
Reaction temperature is 20 DEG C -30 DEG C.
10. iodine selenium thermochemical cycles nitrogen as described in claim 1 restores hydrogen production process, it is characterised in that the step (3)
Middle reaction temperature is 400 DEG C -500 DEG C.
11. iodine selenium thermochemical cycles nitrogen as described in claim 1 restores hydrogen production process, it is characterised in that the step (4)
Middle reaction temperature is 100 DEG C -200 DEG C.
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