CN108342743B - Method and device for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide - Google Patents
Method and device for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide Download PDFInfo
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Abstract
The invention relates to a method and a device for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide, wherein acid gas containing hydrogen sulfide and absorption liquid react in an absorption reactor to produce sulfur, the sulfur enters a sulfur slurry storage tank and then enters a sulfur melting and refining tank for melting and purifying to obtain high-purity sulfur; the filtrate obtained by filtering the clear solution after the reaction enters the anode of the electrolytic reactor for regeneration and then is recycled, and the cathode generates high-purity hydrogen. The invention improves the absorption rate and absorption rate of hydrogen sulfide and the electrolytic efficiency of the electrolytic cell, avoids the blockage of sulfur to the device while not increasing the sulfur separation load, and obtains sulfur and hydrogen with higher purity. The invention eliminates the hydrogen sulfide pollution and brings good economic benefit. The invention has simple process flow and mild operation condition.
Description
Technical Field
The invention relates to a method and a device for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide.
Background
In the process of economic development, the national attention on environmental protection is increasing, hydrogen sulfide is a product in the process of processing petroleum and natural gas, and if the hydrogen sulfide is directly discharged into the atmosphere without being treated, the environment can be seriously polluted, particularly, in recent years, the continuous emergence of high-sulfur-content gas fields and the hydrodesulfurization process commonly adopted in the petrochemical industry for preparing high-quality fuel oil also generate a large amount of hydrogen sulfide gas every day, so national regulations put strict requirements on the treatment of the hydrogen sulfide in corresponding industries.
At present, the most widely used hydrogen sulfide treatment technology is to recover sulfur by a catalytic oxidation method by using a claus device, but hydrogen resources in the sulfur are oxidized into water to be consumed, so that the hydrogen resources are wasted, and the hydrogen energy is a recognized clean energy and hopefully replaces future fossil energy in terms of energy conservation and comprehensive utilization of resources. Therefore, more and more researches are made on the reasonable utilization of abundant hydrogen sulfide resources to prepare hydrogen and sulfur. The existing processes for preparing hydrogen and sulfur by decomposing hydrogen sulfide mainly comprise a thermochemical method, a photochemical decomposition method and an electrochemical method, which have the characteristics, but most of the technologies are not mature. In contrast, indirect electrolysis in electrochemical processes is a promising process, and studies have shown that the process technology is feasible and economically promising compared to the claus process.
Most of the existing indirect hydrogen sulfide electrolysis technologies have the problems of low hydrogen sulfide absorption rate, easy sulfur blockage of devices, low electrolysis efficiency and the like. Chinese patent ZL200610058063.8 provides a method for recovering hydrogen and sulfur from hydrogen sulfide gas by combining an internal circulation absorption reactor with a bipolar plate type electrolytic reactor, which better alleviates the problem of sulfur blockage to a gas distributor in the hydrogen sulfide absorption reactor, but the separation of sulfur and absorption liquid adopts a filtering mode, and the method has the problems of large filtering load, unstable separation effect and the like, and can cause fine sulfur particles to deposit in an electrolytic cell after long-term operation, thereby causing the blockage of the electrolytic cell, and the obtained sulfur has low purity and needs further treatment. The bipolar plate type electrolytic reactor has a complicated structure, high production cost and difficulty in expanding production, and thus industrialization is difficult to achieve.
Disclosure of Invention
The invention aims to provide a method and a device for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide, which improve the absorption rate and absorption rate of the hydrogen sulfide and the electrolysis efficiency of an electrolytic cell, avoid the blockage of the device by the sulfur while not increasing the separation load of the sulfur, obtain the sulfur and hydrogen with higher purity, eliminate the pollution of the hydrogen sulfide and bring good economic benefit.
The method for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide comprises the steps of reacting acid gas containing hydrogen sulfide with absorption liquid in an absorption reactor to produce sulfur, feeding the sulfur into a sulfur slurry storage tank, and then feeding the sulfur into a sulfur melting and refining tank for melting and purifying to obtain high-purity sulfur; the filtrate obtained by filtering the clear solution after the reaction enters the anode of the electrolytic reactor for regeneration and then is recycled, and the cathode generates high-purity hydrogen.
The method for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide comprises the following specific steps:
the method comprises the following steps that acidic gas containing hydrogen sulfide and absorption liquid enter an absorption reactor from the bottom of the absorption reactor, the gas is dispersed into fine bubbles, the bubbles are oxidized by the absorption liquid in the absorption reactor to generate sulfur, the sulfur enters a sulfur slurry storage tank, and then enters a sulfur melting and refining tank for melting and purifying to obtain high-purity sulfur; unreacted acid gas containing hydrogen sulfide enters the absorption reactor again after condensation and liquid removal or is discharged after neutralization; after the liquid in the absorption reactor overflows to the absorption liquid storage tank, the liquid part in the absorption liquid storage tank enters the absorption reactor again to participate in the reaction, and the part enters a filter to filter out sulfur and then is subjected to electrolytic regeneration;
wherein, the liquid part in the absorption liquid storage tank is sent to a filter to filter out sulfur, when the pressure drop of the filter reaches 0.2MPa to 0.3MPa, compressed air heated at 130 ℃ to 140 ℃ is used for pressurization and back blowing, so that the sulfur in the filter is blown off to a sulfur slurry storage tank; when the sulfur amount in the sulfur slurry storage tank exceeds half of the capacity of the storage tank, the sulfur slurry is sent to a sulfur melting and refining tank for melting and purification, the sulfur is layered with the absorption liquid after melting, the lower layer is sulfur and is led out from the bottom of the tank, and the upper layer is the absorption liquid and is sent to the absorption liquid storage tank again to wait for reaction;
sending the liquid part in the absorption liquid storage tank to a filter to obtain filtrate, then sending the filtrate into an anolyte storage tank of an electrolysis device, and then sending the filtrate to an electrolytic cell for anodic electrolysis and regeneration; returning the regenerated absorption liquid to an anode liquid storage tank to wait for participating in electrolytic circulation again, and overflowing excessive regeneration liquid to the absorption liquid storage tank to participate in absorption oxidation reaction again; the catholyte of the electrolytic cell comes from a catholyte storage tank, and enters the catholyte storage tank again after electrolysis to wait for electrolysis circulation; hydrogen ions in the anode liquor of the electrolytic cell enter the cathode through the ion exchange membrane and are reduced into hydrogen.
The volume content of hydrogen sulfide in the acid gas is 1-90%, and other gases are nitrogen, methane, olefin and carbon dioxide.
The absorption liquid contains a compound capable of oxidizing hydrogen sulfide without side reactions, the compound can be regenerated under the potential that the anode does not evolve oxygen, the cathode simultaneously evolves hydrogen, and preferably an acidic solution rich in ferric ions and ferrous ions, and the acid is hydrochloric acid or sulfuric acid.
The reaction of the hydrogen sulfide gas and the absorption liquid is carried out under the conditions of normal pressure and 20-80 ℃; the electrolytic reaction of the cathode and the anode in the electrolytic cell is carried out under the conditions of normal pressure and 20-80 ℃.
The device used by the method for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide comprises an absorption liquid storage tank, wherein the absorption liquid storage tank is connected with an absorption reactor through a feeding pipeline, the absorption reactor is connected with a sulfur slurry storage tank through a sulfur slurry guiding pipeline, the absorption reactor is connected with the absorption liquid storage tank through a clear liquid guiding pipeline, the absorption liquid storage tank is connected with a sulfur melting refining tank through a pipeline, and the sulfur melting refining tank is connected back to the sulfur slurry storage tank; the absorption liquid storage tank is connected with the primary filter through a pipeline, the primary filter is connected with the secondary filter through a pipeline, the secondary filter is connected back to the primary filter through a first pipeline, and the first pipeline is connected with the sulfur slurry storage tank through a pipeline; the absorption liquid storage tank is connected with the electrolysis device through a pipeline; the secondary filter is connected with the electrolysis device.
The top end of the absorption reactor is provided with an air outlet pipe.
The absorption liquid storage tank is connected with the sulfur slurry storage tank through a pipeline.
A primary filtrate storage tank is arranged between the primary filter and the secondary filter.
The electrolysis device comprises an anode liquid storage tank, an anode pump, a cathode liquid regeneration residual liquid pump, a cathode liquid regeneration tank, a gas-liquid separator, a cathode liquid storage tank, a cathode pump and an electrolysis cell; the anolyte storage tank is connected with the catholyte regeneration tank, the catholyte regeneration tank is connected with the catholyte storage tank, and the anolyte storage tank and the catholyte storage tank are both connected with the electrolytic cell; the catholyte regeneration tank is connected with the gas-liquid separator; the electrolytic cell is respectively connected with the gas-liquid separator and the anode liquid storage tank through pipelines.
The method for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide comprises the following specific implementation processes:
(1) acid gas containing hydrogen sulfide and absorption liquid in the absorption liquid storage tank enter the absorption reactor from the bottom of the absorption reactor together, the gas is dispersed into fine bubbles, the bubbles freely rise in the absorption reactor and are oxidized by the absorption liquid to generate sulfur, and the sulfur floats to the liquid level under the air flotation action of the bubbles and overflows to the sulfur slurry storage tank; unreacted acid gas containing hydrogen sulfide can enter the absorption reactor again or be discharged after being neutralized after being condensed and liquid removed; the liquid at the lower part of the absorption reactor contains a small amount of sulfur, and the liquid overflows to an absorption liquid storage tank and waits to enter the absorption reactor again for reaction or enter a filter for filtering out the sulfur and then is subjected to electrolytic regeneration.
(2) After the liquid in the absorption reactor overflows to an absorption liquid storage tank, part of the liquid is sent to a filter, and after the pressure drop of the filter reaches 0.2MPa-0.3MPa, the filtered sulfur is pressurized and blown back by compressed air heated at the temperature of 130-140 ℃ so that a sulfur filter cake in the filter is blown off to a sulfur slurry storage tank. When the sulfur amount in the sulfur slurry storage tank exceeds half of the capacity of the storage tank, the sulfur slurry is sent to a sulfur melting and refining tank for melting and purification, the sulfur is layered with the absorption liquid after melting, the lower layer is sulfur and is led out from the bottom of the tank, and the upper layer is the absorption liquid and is sent to the absorption liquid storage tank again to wait for reaction;
(3) sending the liquid part in the absorption liquid storage tank to a filter to obtain filtrate, then sending the filtrate into an anolyte storage tank of an electrolysis device, and then sending the filtrate to an electrolytic cell for anodic electrolysis and regeneration; returning the regenerated absorption liquid to an anode liquid storage tank to wait for participating in electrolytic circulation again, and overflowing excessive regeneration liquid to the absorption liquid storage tank to participate in absorption oxidation reaction again; the catholyte of the electrolytic cell comes from a catholyte storage tank, and enters the catholyte storage tank again after electrolysis to wait for electrolysis circulation; hydrogen ions in the anode liquor of the electrolytic cell enter the cathode through the ion exchange membrane and are reduced into hydrogen.
And collecting and utilizing the hydrogen after passing through a gas-liquid separator. After long-term electrolytic operation, the catholyte changes, and needs to be pumped into a catholyte regeneration tank for regeneration.
Aiming at the problems of low hydrogen sulfide absorption rate in an absorption reactor, easy sulfur blockage of a device, low electrolysis efficiency of an electrolytic cell and the like, the invention jointly adopts the absorption reactor, a sulfur filter, a sulfur melting refining tank and an electrolytic reactor in operation to prepare high-purity hydrogen and sulfur from hydrogen sulfide.
The present invention belongs to the technology of treating acid gas containing hydrogen sulfide.
Compared with the prior art, the invention has the following beneficial effects:
the method and the device for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide improve the absorption rate and absorption rate of hydrogen sulfide and the electrolysis efficiency of an electrolytic cell, avoid the blockage of the device by sulfur without increasing the separation load of sulfur, and obtain high-purity sulfur and hydrogen. The invention eliminates the hydrogen sulfide pollution and brings good economic benefit. The invention has simple process flow and mild operation condition.
Drawings
FIG. 1 is a process flow diagram of the present invention.
In the figure 1, 1-absorption reactor, 101-sulfur slurry guiding pipeline, 102-clear liquid guiding pipeline, 103-feeding pipeline, 104-residual liquid guiding pipeline, 105-first pipeline, 2-absorption liquid circulating pump, 3-absorption liquid storage tank, 4-filter pump a, 5-sulfur slurry storage tank, 6-clear liquid pump, 7-slurry pump, 8-primary filter, 9-primary filtrate storage tank, 10-filter pump b, 11-sulfur melting refining tank, 12-secondary filter, 13-anolyte storage tank, 14-anolyte pump, 15-catholyte regeneration residual liquid pump, 16-catholyte regeneration tank, 17-gas-liquid separator, 18-catholyte storage tank, 19-catholyte pump and 20-electrolytic cell.
Detailed Description
The present invention will be further described with reference to the following examples.
The following examples were all operated according to the following apparatus and process:
acid gas containing hydrogen sulfide and absorption liquid enter an absorption reactor 1 from the bottom, the gas is dispersed into fine bubbles, the bubbles are oxidized by the absorption liquid in the absorption reactor 1 to generate sulfur, the sulfur enters a sulfur slurry storage tank 5, and then enters a sulfur melting and refining tank 11 for melting and purifying to obtain high-purity sulfur; unreacted acid gas containing hydrogen sulfide enters the absorption reactor 1 again after condensation and liquid removal or is discharged after neutralization; after the liquid in the absorption reactor 1 overflows to the absorption liquid storage tank 3, the liquid part in the absorption liquid storage tank 3 enters the absorption reactor 1 again to participate in the reaction, and the liquid part enters a filter to filter out sulfur and then is subjected to electrolytic regeneration;
wherein, the liquid part in the absorption liquid storage tank 3 is sent to a filter to filter out sulfur, and when the pressure drop of the filter reaches 0.3MPa, compressed air heated at 135 ℃ is used for pressurization and back blowing, so that the sulfur in the filter is blown off to a sulfur slurry storage tank 5; when the sulfur amount in the sulfur slurry storage tank 5 exceeds half of the storage tank capacity, the sulfur slurry is sent to a sulfur melting and refining tank 11 for melting and purification, the sulfur is layered with the absorption liquid after melting, the lower layer is sulfur and is led out from the bottom of the tank, the upper layer is the absorption liquid and is sent to the absorption liquid storage tank 3 again to wait for reaction;
the liquid part in the absorption liquid storage tank 3 is sent to a filter, and the obtained filtrate enters an anode liquid storage tank 13 of the electrolysis device and then is sent to an electrolytic cell 20 for anode electrolysis and regeneration; the regenerated absorption liquid returns to the anode liquid storage tank 13 to wait for participating in the electrolytic cycle again, and the excessive regeneration liquid overflows to the absorption liquid storage tank 3 to participate in the absorption oxidation reaction again; the catholyte of the electrolytic cell 20 comes from the catholyte storage tank 18, and enters the catholyte storage tank 18 again after electrolysis to wait for electrolysis circulation; the hydrogen ions in the anolyte of the electrolytic cell 20 enter the cathode through the ion exchange membrane and are reduced into hydrogen gas.
The volume content of hydrogen sulfide in the acid gas is 1-90%, and other gases are nitrogen, methane, olefin and carbon dioxide.
The absorption liquid is an acidic solution rich in ferric ions and ferrous ions, and the acid is hydrochloric acid or sulfuric acid.
The device used in the method for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide comprises an absorption liquid storage tank 3, wherein the absorption liquid storage tank 3 is connected with an absorption reactor 1 through a feeding pipeline 103, the absorption reactor 1 is connected with a sulfur slurry storage tank 5 through a sulfur slurry outlet pipeline 101, the absorption reactor 1 is connected with the absorption liquid storage tank 3 through a clear liquid outlet pipeline 102, the absorption liquid storage tank 3 is connected with a sulfur melting refining tank 11 through a pipeline, and the sulfur melting refining tank 11 is connected back to the sulfur slurry storage tank 5; the absorption liquid storage tank 3 is connected with a primary filter 8 through a pipeline, the primary filter 8 is connected with a secondary filter 12 through a pipeline, the secondary filter 12 is connected back to the primary filter 8 through a first pipeline 105, and the first pipeline 105 is connected with the sulfur slurry storage tank 5 through a pipeline; the absorption liquid storage tank 3 is connected with an electrolysis device through a pipeline; the secondary filter 12 is connected with an electrolysis device.
The top end of the absorption reactor 1 is provided with an air outlet pipe.
The absorption liquid storage tank 3 is connected with a sulfur slurry storage tank 5 through a pipeline.
A primary filtrate storage tank 9 is arranged between the primary filter 8 and the secondary filter 12.
The electrolysis device comprises an anode liquid storage tank 13, an anode pump 14, a cathode liquid regeneration residual liquid pump 15, a cathode liquid regeneration tank 16, a gas-liquid separator 17, a cathode liquid storage tank 18, a cathode pump 19 and an electrolysis cell 20; the anolyte storage tank 13 is connected with the catholyte regeneration tank 16, the catholyte regeneration tank 16 is connected with the catholyte storage tank 18, and both the anolyte storage tank 13 and the catholyte storage tank 18 are connected with the electrolytic cell 20; the catholyte regeneration tank 16 is connected with a gas-liquid separator 17; the electrolytic cell 20 is connected with the gas-liquid separator 17 and the anolyte storage tank 13 through pipelines, respectively.
The upper part of the absorption reactor 1 is provided with a residual gas outlet and a sulfur slurry outlet, sulfur enters a sulfur slurry storage tank 5 from the residual gas outlet, the middle upper part of the absorption reactor is provided with a clear liquid outlet, clear liquid returns to an absorption liquid storage tank 3 from the clear liquid outlet, and the bottom of the absorption reactor is provided with a feed inlet and a residual liquid outlet respectively.
The sulfur melting refining tank 11 is a corrosion-resistant and pressure-resistant glass lining reaction tank, a liquid level meter is arranged in the tank to facilitate liquid level detection, and a sulfur guide outlet and an absorption liquid guide outlet are arranged at the bottom of the tank.
The specific process flow of the invention is shown in figure 1, and the specific operation is as follows:
the absorption liquid from the absorption liquid storage tank 3 is mixed with the hydrogen sulfide-containing acid gas at the apparatus having a spraying function while being fed to the absorption reactor 1 by the absorption liquid circulation pump 2, and reaches the absorption reactor 1 through the feed line 103. Under the action of injection, gas is dispersed into fine bubbles, the bubbles freely rise in the absorption reactor 1 and react with absorption liquid to generate sulfur, the sulfur floats up to the liquid level under the action of air flotation of the bubbles and overflows to a sulfur slurry storage tank 5 through a sulfur slurry guide pipeline 101, and unabsorbed gas is condensed from the top to remove liquid and then enters an alkaline washing device. The clear liquid in the absorption reactor 1 flows back to the absorption liquid storage tank 3 through the clear liquid lead-out pipeline 102 and waits for the reaction to be carried out again. And a residual liquid outlet pipeline 104 is arranged at the lower part of the absorption reactor 1.
The bottom of the absorption liquid storage tank 3 is provided with two channels, firstly, the absorption liquid is conveyed to the absorption reactor 1 under the action of the absorption liquid circulating pump 2 to participate in the reaction again; secondly, the absorption liquid is conveyed to the primary filter 8 and the secondary filter 12 under the action of the filter pump a to be filtered to remove the solid sulfur. The primary filtrate first enters the primary filtrate tank 9, then is sent by the filter pump b to the secondary filter 12, and finally reaches the anolyte tank 13. After the pressure drop of the filter reaches 0.3MPa, compressed air heated to 135 ℃ is used for pressurizing and back blowing, so that the sulfur filter cake in the primary filter 8 is blown off and sent to the sulfur slurry storage tank 5.
The sulfur slurry in the sulfur slurry storage tank 5 is sent into a sulfur melting refining tank 11 by a slurry pump 7, the heated sulfur is melted into liquid and is layered with the absorption liquid, the liquid sulfur is settled to the bottom of the tank and is discharged, and the absorption liquid at the upper layer is sent to the absorption liquid storage tank 3 by a clear liquid pump 6 to participate in the reaction again.
The absorption liquid in the anolyte storage tank 13 is sent to the anode of the electrolytic cell 20 for anodic oxidation regeneration through the anode pump 14, the regenerated anolyte returns to the anolyte storage tank 13 to wait for participating in the electrolytic cycle again, and meanwhile, the anolyte in the anolyte storage tank 13 overflows to the absorption liquid storage tank 3 to be used as the regenerated absorption liquid; hydrogen ions at the anode enter the cathode through an ion exchange membrane and are reduced into hydrogen at the cathode, catholyte is sent into an electrolytic cell through a cathode pump 19 to be electrolyzed and then enters a catholyte storage tank 18 to wait for electrolysis circulation, and the hydrogen escapes after passing through a gas-liquid separator (17) and can be collected and utilized.
The catholyte in the catholyte storage tank 18 needs to be regenerated after long-term electrolytic operation, the catholyte is distilled periodically, the distilled components are condensed and then flow back to the catholyte storage tank 18, and the residual liquid is sent to the anolyte storage tank 13 by the catholyte regeneration residual liquid pump 15 to be used as anolyte. The catholyte distillation is carried out in a catholyte regeneration tank 16, the catholyte regeneration tank 16 and a catholyte storage tank 18 being connected in series and controlled by respective tube valves.
By containing Fe3+And Fe2+The acid solution is used as absorption liquid to measure the hydrogen sulfide absorption rate, sulfur purity, electrolysis regeneration efficiency and hydrogen production rate under different reaction conditions.
Example 1
Measuring the hydrogen sulfide absorption rate and the sulfur purity at different gas-liquid flow rates:
the absorption reaction is normal pressure, the temperature is 20-40 ℃, the content of hydrogen sulfide in acid gas is 40% (other gases are nitrogen), and Fe in absorption liquid3+At a concentration of about 0.6M, Fe2+The concentration is about 0.3M and the hydrogen ion concentration is about 8M. Changing the flow rate of hydrogen sulfide acid gas to be 20-80L/h, the liquid phase flow rate to be 300-800L/h, controlling the liquid/gas volume ratio to be within the range of 10-15, and measuring the hydrogen sulfide absorption rate and sulfur under different gas-liquid flow ratesThe purity of the sulphur.
The results of the experiment are shown in table 1.
TABLE 1 hydrogen sulfide absorption Rate and Sulfur purity at different gas-liquid flow rates
| Gas/liquid flow rate, L/ |
20/300 | 30/300 | 40/500 | 50/500 | 60/800 | 70/800 | 80/800 |
| Absorption rate of hydrogen sulfide,%) | 99.4 | 99.3 | 99.5 | 99.2 | 99.1 | 99.2 | 99.0 |
| Purity of sulfur% | 99.8 | 99.6 | 99.6 | 99.6 | 99.7 | 99.8 | 99.7 |
It can be seen that the hydrogen sulfide absorption rate has a certain difference under different gas-liquid flow rates, and the hydrogen sulfide absorption rate is comprehensively influenced by a plurality of factors such as the size of bubbles (namely gas-liquid contact area) under different flow rates, the retention time of the bubbles in the absorption liquid, the gas-liquid volume ratio and the like; the gas-liquid flow rate has little influence on the sulfur purity, and although the sulfur generated in the absorption reaction process is influenced by the absorption conditions, the sulfur purity obtained after the melting and purification of the sulfur melting and refining tank is very high.
Example 2
Measuring the hydrogen sulfide absorption rate and the sulfur purity under different hydrogen sulfide contents:
the absorption reaction is normal pressure, the temperature is 20-40 ℃, and Fe in absorption liquid3+Concentration of about 0.6M, Fe in absorption liquid2+The concentration is about 0.3M and the hydrogen ion concentration is about 6M. The flow rate of the fixed hydrogen sulfide-containing acid gas is 40L/h, the flow rate of the liquid phase is 500L/h, and the hydrogen sulfide absorption rate and the sulfur purity under different hydrogen sulfide contents are measured. The results of the experiment are shown in table 2.
TABLE 2 hydrogen sulfide absorption rate and Sulfur purity at different Hydrogen sulfide content
| Hydrogen sulfide content,% | 5 | 20 | 40 | 50 | 60 | 70 | 90 |
| Absorption rate of hydrogen sulfide,%) | 99.0 | 99.2 | 99.2 | 99.3 | 99.3 | 99.3 | 99.5 |
| Purity of sulfur% | 99.6 | 99.7 | 99.7 | 99.8 | 99.7 | 99.9 | 99.5 |
The results show that the hydrogen sulfide absorption rate increases with increasing hydrogen sulfide content in the acid gas; the purity of the sulfur after melting and purification is also slightly influenced by the content of the hydrogen sulfide, which also shows that the purification effect of the sulfur melting and refining tank is obvious.
Example 3
Measuring the hydrogen sulfide absorption rate and the sulfur purity at different reaction temperatures:
the absorption reaction is normal pressure, the content of hydrogen sulfide in acid gas is 50 percent, and Fe in absorption liquid3+Concentration of about 0.55M, Fe2+Concentration of about 0.1M, hydrogen ion concentrationThe degree of the sulfur absorption is about 5M, the flow rate of the hydrogen sulfide-containing acid gas is 40L/h, the flow rate of the absorption liquid is 400L/h, and the hydrogen sulfide absorption rate and the sulfur purity at different reaction temperatures are measured. The results of the experiments are shown in the following table.
TABLE 3 hydrogen sulfide absorption rate and Sulfur purity at different reaction temperatures
| Absorption of reaction temperature, DEG C | 30 | 40 | 50 | 60 | 70 | 80 |
| Absorption rate of hydrogen sulfide,%) | 99.1 | 99.2 | 99.2 | 99.4 | 99.2 | 99.5 |
| Purity of sulfur% | 99.8 | 99.7 | 99.9 | 99.8 | 99.6 | 99.7 |
The result shows that the absorption rate of the hydrogen sulfide is increased along with the increase of the temperature, because the reaction rate constant can be increased by increasing the temperature, the reaction is accelerated, and meanwhile, the temperature increase is beneficial to reducing the viscosity of the absorption liquid, increasing the diffusion coefficient of the hydrogen sulfide in the absorption liquid and being beneficial to the reaction. The temperature has obvious influence on the purity of the sulfur, the generation rate of the sulfur is high at high temperature, and the supersaturation degree in the absorption liquid is high, so that the sulfur particles are small and are not easy to wrap impurities, and on the contrary, the sulfur obtained at low temperature contains more impurities. But most of impurities in the sulfur are remained in the absorption liquid after the melting purification.
Example 4
Determining the regeneration efficiency and hydrogen production rate of the electrolytic cell to the absorption liquid:
the absorption reaction is normal pressure, the absorption reaction temperature is about 30 ℃, the gas-liquid flow rates are respectively 45L/h and 450L/h, the content of hydrogen sulfide in acid gas is 30%, the concentration of hydrogen ions in absorption liquid is 5M, and Fe3+And Fe2+The concentrations of (A) and (B) were 0.28M and 0.65M, respectively, the cell temperature was 30 to 50 ℃ and the cell voltage was 1.2V, and the absorption liquid regeneration efficiency and the hydrogen generation rate during the electrolysis reaction were measured for 24 hours. Absorbing Fe in the solution after 24 hours of reaction3+And Fe2+The content of (B) is 0.278M and 0.648M respectively, the regeneration efficiency of the absorption solution is 99.3%, but the absorption solution has slight loss because the generated sulfur has iron ions, the hydrogen generation rate in the whole process is kept at 13.3-13.5L/h, and the hydrogen purity is about 100%.
The method has the advantages of simple process flow and mild operation conditions, and can be seen from the above embodiments, the method has obvious effect of treating the acid gas containing hydrogen sulfide, the absorption rate of the hydrogen sulfide is more than 99%, the obtained sulfur and hydrogen have high purity, the requirement range for the gas-liquid flow, the hydrogen sulfide content in the acid gas and the like is wide, good reference is provided for the treatment of the hydrogen sulfide, good economic benefits are obtained, and the method is more beneficial to environmental protection, so the method has potential application prospects.
Claims (6)
1. A method for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide is characterized by comprising the following specific steps:
acid gas containing hydrogen sulfide and absorption liquid enter the absorption reactor (1) from the bottom of the absorption reactor (1), the gas is dispersed into fine bubbles, the bubbles are oxidized by the absorption liquid in the absorption reactor (1) to generate sulfur, the sulfur enters a sulfur slurry storage tank (5), and then enters a sulfur melting and refining tank (11) for melting and purifying to obtain high-purity sulfur; unreacted acid gas containing hydrogen sulfide enters the absorption reactor (1) again after condensation and liquid removal or is discharged after neutralization; after the liquid in the absorption reactor (1) overflows to the absorption liquid storage tank (3), the liquid part in the absorption liquid storage tank (3) enters the absorption reactor (1) again to participate in the reaction, and the part enters a filter to filter out sulfur and then is subjected to electrolytic regeneration;
the flow rate of the acid gas containing hydrogen sulfide is 20-80L/h, the flow rate of the liquid phase is 300-800L/h, and the volume ratio of the liquid to the gas is controlled within the range of 10-15;
wherein, the liquid part in the absorption liquid storage tank (3) is sent to a filter to filter out sulfur, and when the pressure drop of the filter reaches 0.2MPa to 0.3MPa, compressed air heated at 130 ℃ to 140 ℃ is used for pressurization and back blowing, so that the sulfur in the filter is blown off to a sulfur slurry storage tank (5); when the sulfur amount in the sulfur slurry storage tank (5) exceeds half of the storage tank capacity, the sulfur slurry is sent to a sulfur melting and refining tank (11) for melting and purification, the sulfur is separated from the absorption liquid after melting, the lower layer is sulfur and is led out from the bottom of the tank, and the upper layer is the absorption liquid and is sent to the absorption liquid storage tank (3) again to wait for reaction;
the liquid part in the absorption liquid storage tank (3) is sent to a filter, and the obtained filtrate enters an anode liquid storage tank (13) of the electrolysis device and then is sent to an electrolytic cell (20) for anode electrolysis regeneration; the regenerated absorption liquid returns to the anode liquid storage tank (13) to wait for participating in the electrolytic cycle again, and the excessive regeneration liquid overflows to the absorption liquid storage tank (3) to participate in the absorption oxidation reaction again; the catholyte of the electrolytic cell (20) comes from the catholyte storage tank (18), and enters the catholyte storage tank (18) again after electrolysis to wait for electrolysis circulation; hydrogen ions in the anode liquid of the electrolytic cell (20) enter the cathode through the ion exchange membrane and are reduced into hydrogen;
the volume content of hydrogen sulfide in the acid gas is 1-90%, and other gases are nitrogen, methane, olefin and carbon dioxide;
the absorption liquid is an acidic solution rich in ferric ions and ferrous ions, and the acid is hydrochloric acid or sulfuric acid;
the device used in the method for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide comprises an absorption liquid storage tank (3), and is characterized in that the absorption liquid storage tank (3) is connected with an absorption reactor (1) through a feeding pipeline (103), the absorption reactor (1) is connected with a sulfur slurry storage tank (5) through a sulfur slurry guiding pipeline (101), the absorption reactor (1) is connected with the absorption liquid storage tank (3) through a clear liquid guiding pipeline (102), the absorption liquid storage tank (3) is connected with a sulfur melting refining tank (11) through a pipeline, and the sulfur melting refining tank (11) is connected back to the sulfur slurry storage tank (5); the absorption liquid storage tank (3) is connected with the primary filter (8) through a pipeline, the primary filter (8) is connected with the secondary filter (12) through a pipeline, the secondary filter (12) is connected back to the primary filter (8) through a first pipeline (105), and the first pipeline (105) is connected with the sulfur slurry storage tank (5) through a pipeline; the absorption liquid storage tank (3) is connected with the electrolysis device through a pipeline; the secondary filter (12) is connected with the electrolysis device.
2. The method for preparing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide as claimed in claim 1, wherein the reaction of hydrogen sulfide gas and absorption liquid is carried out under normal pressure at 20-80 ℃; the electrolytic reaction of the cathode and the anode in the electrolytic cell is carried out under the conditions of normal pressure and 20-80 ℃.
3. The method for producing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide as claimed in claim 1, wherein the top end of the absorption reactor (1) is provided with an outlet pipe.
4. The process for producing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide as claimed in claim 1, wherein the absorbing liquid tank (3) is connected to the sulfur slurry tank (5) through a pipeline.
5. The process for the electrolysis of hydrogen sulphide for the production of high purity hydrogen and sulphur according to claim 1, wherein a primary filtrate tank (9) is arranged between the primary filter (8) and the secondary filter (12).
6. The method for producing high-purity hydrogen and sulfur by electrolyzing hydrogen sulfide as claimed in claim 1, wherein the electrolysis apparatus comprises an anolyte storage tank (13), an anolyte pump (14), a catholyte regeneration residue pump (15), a catholyte regeneration tank (16), a gas-liquid separator (17), a catholyte storage tank (18), a catholyte pump (19), an electrolytic cell (20); the anolyte storage tank (13) is connected with the catholyte regeneration tank (16), the catholyte regeneration tank (16) is connected with the catholyte storage tank (18), and the anolyte storage tank (13) and the catholyte storage tank (18) are both connected with the electrolytic cell (20); the catholyte regeneration tank (16) is connected with the gas-liquid separator (17); the electrolytic cell (20) is respectively connected with the gas-liquid separator (17) and the anolyte storage tank (13) through pipelines.
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| CN111996541B (en) * | 2019-05-27 | 2022-01-04 | 中国石油天然气股份有限公司 | Indirect hydrogen sulfide electrolysis method and device for improving hydrogen yield |
| CN111501056A (en) * | 2020-04-01 | 2020-08-07 | 马艺嘉 | Organic electrolyte for low-temperature electrolysis of hydrogen sulfide to produce hydrogen, and circulating reaction device and process |
| CN114481157A (en) * | 2021-12-15 | 2022-05-13 | 中国科学院大连化学物理研究所 | Full-flow process method for preparing hydrogen and sulfur by electrochemically decomposing hydrogen sulfide with assistance of mediator |
| CN114941142B (en) * | 2022-06-14 | 2023-06-09 | 郑州中科新兴产业技术研究院 | Anolyte for high-efficiency decomposition of hydrogen sulfide and electrolysis and regeneration method thereof |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241648A (en) * | 1999-07-29 | 2000-01-19 | 石油大学(北京) | Preparation of zinc sulfide and hydrogen from hydrogen sulfide |
| CN101028920A (en) * | 2006-02-28 | 2007-09-05 | 中国石油大学(北京) | Method for recovering sulfur and making hydrogen from hydrogen sulfide |
| CN101823699A (en) * | 2009-03-02 | 2010-09-08 | 孙新龙 | Process technology for converting sulfureted hydrogen into elemental sulfur |
| CN102408095A (en) * | 2011-08-20 | 2012-04-11 | 大连理工大学 | Method of decomposing hydrogen sulfide for preparation of hydrogen and elemental sulfur |
| CN102500202A (en) * | 2011-11-21 | 2012-06-20 | 武汉大学 | Indirect electrolysis method for hydrogen sulfide |
| CN102527214A (en) * | 2011-12-23 | 2012-07-04 | 中国石油化工股份有限公司 | Method for removing hydrogen sulfide from gas |
| CN102895870A (en) * | 2012-09-28 | 2013-01-30 | 美景（北京）环保科技有限公司 | Treatment system and treatment method for removing hydrogen sulfide from acid gas |
| CN102921277A (en) * | 2012-10-23 | 2013-02-13 | 中国石油化工股份有限公司 | Hydrogen sulfide tail gas treatment system and method |
| CN103495329A (en) * | 2013-10-18 | 2014-01-08 | 庆华集团新疆和丰能源化工有限公司 | Process for removing hydrogen sulfide and recovering sulphur |
| CN103537176A (en) * | 2013-10-25 | 2014-01-29 | 中国石油化工股份有限公司 | Electrochemical recycling method and electrochemical recycling device for claus tower tail gas by cooperating with absorption liquid |
| CN103768916A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Oxidative desulphurization and brimstone recycling method |
| CN103865602A (en) * | 2014-03-25 | 2014-06-18 | 胡明成 | Wet-process ferric salt membrane-electrolysis regenerated biogas desulfurization method and device thereof |
| CN104607435A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Sulfur-containing alkaline residue comprehensive control method |
| CN104961103A (en) * | 2015-07-10 | 2015-10-07 | 山东三维石化工程股份有限公司 | Sulfur recovery process and apparatus |
| CN105018958A (en) * | 2014-04-22 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for coupled decomposition of hydrogen sulfide through photocatalytic/electrocatalytic-chemical ring reaction |
| CN105695655A (en) * | 2016-04-11 | 2016-06-22 | 北京神雾环境能源科技集团股份有限公司 | System and method for preparing clean gas base vertical furnace reducing gas through coal gasification |
| CN106076083A (en) * | 2016-05-16 | 2016-11-09 | 宁波市协和环境工程有限公司 | A kind of technique of concerted catalysis oxidation system removing hydrogen sulfide Recovered sulphur |
-
2017
- 2017-01-23 CN CN201710050965.5A patent/CN108342743B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241648A (en) * | 1999-07-29 | 2000-01-19 | 石油大学(北京) | Preparation of zinc sulfide and hydrogen from hydrogen sulfide |
| CN101028920A (en) * | 2006-02-28 | 2007-09-05 | 中国石油大学(北京) | Method for recovering sulfur and making hydrogen from hydrogen sulfide |
| CN101823699A (en) * | 2009-03-02 | 2010-09-08 | 孙新龙 | Process technology for converting sulfureted hydrogen into elemental sulfur |
| CN102408095A (en) * | 2011-08-20 | 2012-04-11 | 大连理工大学 | Method of decomposing hydrogen sulfide for preparation of hydrogen and elemental sulfur |
| CN102500202A (en) * | 2011-11-21 | 2012-06-20 | 武汉大学 | Indirect electrolysis method for hydrogen sulfide |
| CN102527214A (en) * | 2011-12-23 | 2012-07-04 | 中国石油化工股份有限公司 | Method for removing hydrogen sulfide from gas |
| CN102895870A (en) * | 2012-09-28 | 2013-01-30 | 美景（北京）环保科技有限公司 | Treatment system and treatment method for removing hydrogen sulfide from acid gas |
| CN102921277A (en) * | 2012-10-23 | 2013-02-13 | 中国石油化工股份有限公司 | Hydrogen sulfide tail gas treatment system and method |
| CN103768916A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Oxidative desulphurization and brimstone recycling method |
| CN103495329A (en) * | 2013-10-18 | 2014-01-08 | 庆华集团新疆和丰能源化工有限公司 | Process for removing hydrogen sulfide and recovering sulphur |
| CN103537176A (en) * | 2013-10-25 | 2014-01-29 | 中国石油化工股份有限公司 | Electrochemical recycling method and electrochemical recycling device for claus tower tail gas by cooperating with absorption liquid |
| CN104607435A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Sulfur-containing alkaline residue comprehensive control method |
| CN103865602A (en) * | 2014-03-25 | 2014-06-18 | 胡明成 | Wet-process ferric salt membrane-electrolysis regenerated biogas desulfurization method and device thereof |
| CN105018958A (en) * | 2014-04-22 | 2015-11-04 | 中国科学院大连化学物理研究所 | Method for coupled decomposition of hydrogen sulfide through photocatalytic/electrocatalytic-chemical ring reaction |
| CN104961103A (en) * | 2015-07-10 | 2015-10-07 | 山东三维石化工程股份有限公司 | Sulfur recovery process and apparatus |
| CN105695655A (en) * | 2016-04-11 | 2016-06-22 | 北京神雾环境能源科技集团股份有限公司 | System and method for preparing clean gas base vertical furnace reducing gas through coal gasification |
| CN106076083A (en) * | 2016-05-16 | 2016-11-09 | 宁波市协和环境工程有限公司 | A kind of technique of concerted catalysis oxidation system removing hydrogen sulfide Recovered sulphur |
Non-Patent Citations (2)
| Title |
|---|
| 从硫化氢中回收氢气和硫磺的方法;罗文利;《石油大学学报》;19940830;第18卷(第4期);第95-100页 * |
| 由硫化氢制取硫磺及氢气扩大试验研究;李发永 等;《化工进展》;20011231(第7期);第38-41页 * |
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