CN108624900B - Method for producing hydrogen by electrolyzing waste liquid coal slurry - Google Patents
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- 239000007788 liquid Substances 0.000 title claims abstract description 88
- 239000003250 coal slurry Substances 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 43
- 239000001257 hydrogen Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003245 coal Substances 0.000 claims abstract description 41
- 239000010815 organic waste Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007667 floating Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000002817 coal dust Substances 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 27
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000001311 chemical methods and process Methods 0.000 description 4
- 239000003034 coal gas Substances 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- -1 metal ions Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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- Water Treatment By Electricity Or Magnetism (AREA)
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Abstract
The invention relates to the field of coal electrochemical hydrogen production and wastewater resource recycling, and aims to provide a method for producing hydrogen by electrolyzing waste liquid coal slurry. The method comprises the following steps: pretreating the organic waste liquid to remove solid impurities, floating oil and substances influencing the conductivity of the electrolyte; uniformly mixing organic waste liquid, coal dust, electrolyte and water to obtain waste liquid coal slurry; the waste coal slurry is moved into an electrolysis device to prepare hydrogen in an electrolysis mode, and the waste coal slurry is kept flowing by using a stirring component in the electrolysis process. The invention can improve the hydrogen production rate of the electrolyzed water in a cheap mode, and also considers the method of waste liquid treatment and the efficient and clean utilization of coal, thereby improving the hydrogen production rate of the electrolyzed coal slurry. Meanwhile, the organic waste liquid has the effects of degrading organic matters and increasing the hydrogen yield. Realizes the resource utilization of the organic wastewater which is difficult to treat, and changes waste into valuable. The investment cost is low, the process steps are simple, and the compatibility with other processes for producing hydrogen by electrolyzing coal slurry is good.
Description
Technical Field
The invention belongs to the field of coal electrochemical hydrogen production and wastewater resource recycling, and particularly relates to a method for producing hydrogen by electrolyzing waste liquid coal slurry.
Background
As an important secondary energy source, hydrogen is regarded as a key in the strategic process of energy in the future, and is increasingly emphasized by people. The hydrogen production technology by electrolyzing coal slurry is widely researched since 1979 Coughlin et al published relevant literature on Nature impurities. Compared with the electrolyzed water, the theoretical electrolytic potential of the electrolyzed coal slurry is 0.21V which is far lower than the theoretical electrolytic potential of the electrolyzed water by 1.23V, the actual energy consumption of the electrolyzed coal slurry is about 50 percent of the energy consumption of the electrolyzed water, and the energy-saving device has obvious energy-saving advantage; compared with the traditional coal gasification hydrogen production method, the hydrogen production method by electrolyzing the coal slurry is carried out in the water solution, and elements such as N, S in the coal can be oxidized and dissolved in the solution, so the method is easy to treat and can not generate NOX，SO2And the like, thereby having obvious environmental protection advantages. However, the reaction rate of hydrogen production by coal slurry electrolysis is still low, and the adoption of clean water makes the hydrogen production cost rise to some extent while the hydrogen production cannot be popularized and applied in places with water resource shortage.
With the rapid development of economy, a large amount of various organic wastewater is generated, and the direct discharge of the wastewater brings serious environmental problems. Because the components of the wastewater are very complex and the recovery and treatment are very difficult, the wastewater becomes a bottleneck problem which restricts the development of industrial economy. At present, various methods for treating high-concentration organic wastewater, such as biochemical treatment, membrane separation, catalytic oxidation and the like, have the defects of high recovery treatment cost, complex process and incomplete treatment, and cannot be accepted by enterprises. In recent years, the preparation of wastewater coal water slurry by mixing wastewater with coal is considered as a novel method for recycling wastewater with low cost and near zero emission. However, the wastewater coal water slurry has the problems of needing special users and limited market capacity.
Based on the reasons, the invention provides a technical method for producing hydrogen by electrolyzing waste liquid coal slurry. On one hand, the interaction of various organic matters, ion elements and the like in the wastewater and coal particles, and the functions of organic matter decomposition, ion catalysis, ion conductivity increase and the like are utilized to improve the hydrogen production rate; on the other hand, the organic wastewater is recycled and reused, and the wastewater is changed into valuables.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a method for producing hydrogen by electrolyzing waste liquid coal slurry.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
the method for producing hydrogen by electrolyzing waste liquid coal slurry comprises the following steps:
(1) pretreating the organic waste liquid to remove solid impurities, floating oil and substances influencing the conductivity of the electrolyte;
the organic waste liquid is any one or a mixture of more of the following substances: washing gas water in a gas washing process, sulfur water in a gas flue gas desulfurization process and carbonized water in an ammonia synthesis process;
(2) uniformly mixing organic waste liquid, coal dust, electrolyte and water to obtain waste liquid coal slurry; in the waste liquid coal slurry, the volume of the organic waste liquid accounts for 5-80%, the concentration of the coal powder is 0.01-0.6 g/mL, and the concentration of the electrolyte is 0.1-4 mol/L;
(3) and (3) transferring the waste liquid coal slurry into an electrolysis device to prepare hydrogen in an electrolysis mode, wherein the waste liquid coal slurry keeps flowing by using a stirring component in the electrolysis process.
In the invention, in the step (2), Fe metal ions provided by soluble salt are added into the waste liquid coal slurry as a catalyst, and the addition concentration is 0.05-0.5 mol/L.
In the present invention, the electrolyte is sulfuric acid.
In the invention, the electrolyte is a stirring component which is mechanical stirring equipment, magnetic stirring equipment or circulating pump equipment.
In the invention, the volume ratio of the organic waste liquid in the waste liquid coal slurry is determined according to the highest current density (namely the highest electrolysis rate) which can be achieved during the hydrogen production by electrolysis.
Description of the inventive principles:
in the invention, the organic waste liquid is used for preparing the waste liquid coal slurry for electrolytic hydrogen production, and the main action mechanism of the invention is that the following synergistic action is utilized: (1) part of organic matters and ionic elements with the function of the surfactant in the organic waste liquid improve the slurrying property and the dispersibility of the coal slurry and promote the action of coal particles and the surface of an electrode; (2) the ions (such as metal ions, Cl ions and the like) with catalytic action in the organic waste liquid have catalytic action on the oxidation of the coal particles; (3) the conductivity of the electrolyte of the waste liquid coal slurry is increased by the conductive ions in the organic waste liquid, so that the current density is improved; (4) the organic matter reaction current in the organic waste liquid increases the total current density.
The organic waste liquid needs to be pretreated before pulping, and the specific pretreatment mode is adjusted according to the components of the waste liquid, such as: removing solid impurities and floating oil by methods of precipitation, filtration and the like; when a substance affecting the conductivity of the electrolyte is removed, for example, when sulfuric acid is used as the electrolyte, a substance that decreases the conductivity by reacting with sulfuric acid, such as carbonate or barium salt, should be removed. The concentration of the organic waste liquid is specifically determined according to the type of the waste liquid, and the aim is to achieve the highest current density (i.e. the maximum electrolysis rate) or the actual production process needs.
Compared with the prior art, the invention has the advantages that:
(1) the invention can improve the hydrogen production rate by electrolyzing water in a cheap way, and also considers the method for treating waste liquid and the high-efficiency clean utilization of coal. The hydrogen production rate of the coal slurry is improved by utilizing the interaction of the effective components in the organic waste liquid and the coal and the catalytic effect of organic matters and ionic elements. Meanwhile, the organic waste liquid has the effects of degrading organic matters and increasing the hydrogen yield. Realizes the resource utilization of the organic wastewater which is difficult to treat, and changes waste into valuable.
(2) The hydrogen is produced by the cooperation of electricity, coal and waste liquid, the effective components in the waste liquid are fully utilized, the interaction with the coal is fully utilized, and the reaction rate of producing hydrogen by electrolyzing water is improved.
(3) Compared with other methods for improving the reaction rate of the electrolytic coal slurry, such as preparation of a catalytic anode and the like, the method for improving the reaction rate of the electrolytic coal slurry by using the waste liquid has the advantages of low investment cost and simple process steps.
(4) The invention improves the reaction rate of the electrolytic coal slurry, and has the effects of degrading organic matters and increasing the hydrogen yield.
(5) The invention has good compatibility with other processes for producing hydrogen by electrolyzing coal slurry.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention.
FIG. 2 is a diagram of an electrolyzer of an embodiment.
Detailed description of the invention
The present invention will be described in further detail with reference to the following drawings and specific examples, but the scope of the present invention is not limited to the following examples.
The flow of the invention is shown in FIG. 1.
The pretreatment of the waste liquid is carried out according to the types and properties of the organic waste liquid and the electrolyte. The wastewater pretreatment process of the following examples was carried out for the types of wastewater used in the examples: firstly, carrying out precipitation pretreatment to remove precipitates; then adding a small amount of dilute sulfuric acid into the wastewater, fully stirring for reaction, filtering by using filter paper when no obvious bubbles are generated and the precipitate is not increased any more, and storing for later use.
Mixing the pretreated organic waste liquid, coal powder, electrolyte and water according to a certain proportion to prepare waste liquid coal slurry, wherein the volume ratio of the organic waste liquid in the waste liquid coal slurry is 5-80%, the concentration of the coal powder is 0.01-0.6 g/mL, and the concentration of the electrolyte is 0.1-4 mol/L. The waste liquid coal slurry is added with Fe ion catalyst (ferric sulfate powder is used as raw material of the ion catalyst in the embodiment), and then is added into an electrolysis device for electrolysis hydrogen production.
For convenient and accurate representation, the usage amount of each raw material component when preparing the waste liquid coal slurry is described as follows: the usage of the organic waste liquid is expressed by the volume percentage of the organic waste liquid in the waste liquid coal slurry, and the unit percent is; the dosage of the electrolyte is described by the molar concentration of the electrolyte in the waste liquid coal slurry, and the unit mol/L is; the dosage of the coal powder is described by the ratio of the mass of the coal powder to the total volume of the waste liquid coal slurry, and the unit is g/mL; the Fe ions are described by the molar concentration of the Fe ions in the waste liquid coal slurry, and the unit mol/L is.
The electrolysis apparatus of the following example is shown in FIG. 2. An H-shaped glass electrolytic cell is adopted, a platinum mesh electrode is adopted as an anode electrode 1, a platinum mesh electrode is also adopted as a cathode counter electrode 2, a positive electrolytic cell and a negative electrolytic cell are separated by a Nafion117 proton exchange membrane 3, the anode electrolytic cell is stirred by a magnetic stirring device 4 (in examples 4 and 5, mechanical stirring and circulating pump electrolytic cells with the same specification are adopted), a water bath 5 ensures the constant temperature of the electrolytic process, and cathode and anode electrolytic gases are led out through gas guide holes 6 and 7.
Example 1
In the embodiment, waste water coal water slurry prepared from coal chemical process waste water-coal gas washing process waste water (referred to as gas washing water for short) is electrolyzed to prepare hydrogen.
The pretreated gas washing water, coal powder, sulfuric acid, water and ferric sulfate powder are fully mixed to prepare the gas washing water waste liquid coal slurry with the gas washing water concentration of 5 percent, the coal powder concentration of 0.01g/mL, the sulfuric acid concentration of 0.1mol/L and the Fe ion concentration of 0.05 mol/L. The results of electrolysis under the catalysis of Fe ions at a constant voltage of 1.1V are shown in Table 1, No. 1.
The serial number 1.1 is the result of electrolyzing coal slurry without adding waste liquid under the same condition; no. 1.2 shows the result of the same conditions without Fe ion catalysis.
Example 2
In the embodiment, waste water coal water slurry prepared from coal chemical process waste water-coal gas washing process waste water (referred to as gas washing water for short) is electrolyzed to prepare hydrogen.
The pretreated gas washing water, coal powder, sulfuric acid, water and ferric sulfate powder are fully mixed to prepare the gas washing water waste liquid coal slurry with the concentration of the gas washing water being 10 percent, the concentration of the coal powder being 0.1g/mL, the concentration of the sulfuric acid being 1mol/L and the concentration of the Fe ions being 0.1 mol/L. The results of electrolysis under the catalysis of Fe ions at a constant voltage of 1.1V are shown in Table 1, No. 2.
The serial number 2.1 is the result of electrolyzing coal slurry without adding waste liquid under the same condition; no. 2.2 shows the result of the same conditions without Fe ion catalysis.
Example 3
In the embodiment, waste water coal water slurry prepared from coal chemical process wastewater-coal gas and flue gas desulfurization process wastewater (sulfur water for short) is used for electrolytic hydrogen production.
The pretreated sulfur water, coal powder, sulfuric acid, water and ferric sulfate powder are fully mixed to prepare the sulfur water waste liquid coal slurry with the sulfur water concentration of 50 percent, the coal powder concentration of 0.1g/mL, the sulfuric acid concentration of 1mol/L and the Fe ion concentration of 0.5 mol/L. The results of electrolysis under a constant pressure of 1.1V under the catalysis of Fe ions are shown in Table 1, No. 3.
The serial number 3.1 is the result of electrolyzing coal slurry without adding waste liquid under the same condition; no. 3.2 shows the result of the same conditions without Fe ion catalysis.
Example 4
In the embodiment, waste water coal water slurry prepared from coal chemical process wastewater-coal gas and flue gas desulfurization process wastewater (sulfur water for short) is used for electrolytic hydrogen production.
The pretreated sulfur water, coal powder, sulfuric acid, water and ferric sulfate powder are fully mixed to prepare the sulfur water waste liquid coal slurry with the sulfur water concentration of 75 percent, the coal powder concentration of 0.4g/mL, the sulfuric acid concentration of 2mol/L and the Fe ion concentration of 0.1 mol/L. Under the catalysis of Fe ions, electrolysis was carried out at a constant pressure of 1.1V with mechanical stirring, and the electrolysis results are shown in Table 1, No. 4.
The serial number 4.1 is the result of electrolyzing coal slurry without adding waste liquid under the same condition; no. 4.2 shows the result of the same conditions without Fe ion catalysis.
Example 5
In the embodiment, waste water coal water slurry prepared from wastewater in the ammonia synthesis process, namely carbonized water (referred to as carbonized water for short) is used for preparing hydrogen by electrolysis.
The pretreated sulfur water, coal powder, sulfuric acid, water and ferric sulfate powder are fully mixed to prepare carbonized water waste liquid coal slurry with the carbonized water concentration of 80 percent, the coal powder concentration of 0.6g/mL, the sulfuric acid concentration of 4mol/L and the Fe ion concentration of 0.05 mol/L. Under the catalysis of Fe ions, electrolysis was carried out at a constant voltage of 1.1V under the stirring of a circulating pump, and the electrolysis results are shown in Table 1, No. 5.
The serial number 5.1 is the result of electrolyzing coal slurry without adding waste liquid under the same condition; no. 5.2 shows the result of the same conditions without Fe ion catalysis.
TABLE 1 Current Density of electrolytic waste liquid coal slurry under different conditions
As can be seen from Table 1, the current densities of the waste liquid coal slurry added with the electrolytic washing water and the waste liquid coal slurry added with the sulfur water during electrolysis are obviously higher compared with the electrolytic coal slurry without the organic waste liquid under the same conditions; and the current density of the waste liquid coal slurry added with the electrolytic carbonized water is increased to a smaller extent during electrolysis. This aspect shows that the addition of the waste liquid is indeed beneficial to increase the reaction rate of the electrolytic coal slurry; on the other hand, it is explained that the effect of increasing the hydrogen production rate is related to the kind of the organic waste liquid added. The reason for this is that the interaction effect between the organic matter and the ionic element in the organic waste liquid and the coal is different from the oxidative decomposition effect of the organic matter in the organic waste liquid. In addition, as the concentration of the organic waste liquid increases, the electrolytic current density tends to increase first and then decrease slowly, which indicates that the concentration of the organic waste liquid is not as high as possible, and has an optimal value. And the existence of Fe ions obviously increases the current density, which shows that the Fe ions have obvious catalytic action on the electrolytic waste liquid coal slurry.
Therefore, the method successfully utilizes the waste liquid to improve the hydrogen production rate of the electrolytic coal slurry reaction, gives consideration to the treatment of the waste water, and achieves the benefit of changing waste into valuables.
Claims (4)
1. A method for producing hydrogen by electrolyzing waste liquid coal slurry is characterized by comprising the following steps:
(1) pretreating the organic waste liquid to remove solid impurities, floating oil and substances influencing the conductivity of the electrolyte;
the organic waste liquid is any one or a mixture of more of the following substances: washing gas water in a gas washing process, sulfur water in a gas flue gas desulfurization process and carbonized water in an ammonia synthesis process;
(2) uniformly mixing organic waste liquid, coal dust, electrolyte and water to obtain waste liquid coal slurry; in the waste liquid coal slurry, the volume of the organic waste liquid accounts for 5-80%, the concentration of the coal powder is 0.01-0.6 g/mL, and the concentration of the electrolyte is 0.1-4 mol/L; then, adding Fe metal ions provided by soluble salt into the waste liquid coal slurry as a catalyst, wherein the addition concentration is 0.05-0.5 mol/L;
(3) and (3) transferring the waste liquid coal slurry into an electrolysis device to prepare hydrogen in an electrolysis mode, wherein the waste liquid coal slurry keeps flowing by using a stirring assembly in the electrolysis process.
2. The method of claim 1, wherein the electrolyte is sulfuric acid.
3. The method of claim 1, wherein the stirring assembly is a mechanical stirring device, a magnetic stirring device, or a circulating pump device.
4. The method of claim 1, wherein the volume fraction of the organic waste liquid in the waste coal slurry is determined based on the highest current density achievable during the electrolytic hydrogen production.
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