CN109929636B - Biogas desulfurization method and device - Google Patents
Biogas desulfurization method and device Download PDFInfo
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- CN109929636B CN109929636B CN201711377764.2A CN201711377764A CN109929636B CN 109929636 B CN109929636 B CN 109929636B CN 201711377764 A CN201711377764 A CN 201711377764A CN 109929636 B CN109929636 B CN 109929636B
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Abstract
The invention provides a biogas desulfurization method and a device, and the method comprises the following steps: mixing the marsh gas with a desulfurization solution to enable the marsh gas to be micro-foamed, and then carrying out desulfurization reaction; carrying out gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurization liquid to obtain desulfurized biogas and a sulfur-containing desulfurization liquid; drying and purifying the desulfurized biogas; and (3) carrying out desulfurization regeneration treatment on the sulfur-containing desulfurization solution under the action of a metal phthalocyanine catalyst and oxygen, and recycling the sulfur-containing desulfurization solution after the regeneration treatment after separation treatment. The device includes: the device comprises a gas-liquid mixing device provided with a feed inlet and a discharge outlet, a reactor with an inlet communicated with the discharge outlet of the gas-liquid mixing device, a gas-liquid separation tank communicated with the reactor, a drying and purifying device communicated with the gas-liquid separation tank, and a regenerating device respectively communicated with the gas-liquid mixing device and the gas-liquid separation tank. The method and the device can increase the contact area, improve the desulfurization efficiency and reduce the loss of the catalyst.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a biogas desulfurization method and a biogas desulfurization device.
Background
The biogas is taken as renewable clean energy, and is gradually valued by society under the condition that the pollution problem is increasingly prominent. Since biogas generally contains hydrogen sulfide gas and is likely to generate harmful substances such as sulfur dioxide after combustion, it is necessary to subject biogas to desulfurization treatment before use.
At present, domestic processes for biogas desulfurization can be specifically divided into three types, namely biological desulfurization, dry desulfurization and wet desulfurization. Among them, the biological desulfurization is a process of using microorganisms or enzymes contained therein to catalyze sulfur-containing compounds and release the sulfur contained therein, and is roughly classified into She11-Paques process, Bio-SR process, and biochemical ferric-alkali solution catalysis method. The biological desulfurization has the advantages of no need of catalyst and oxidant, no need of treating chemical sludge, little biological pollution, low energy consumption, high efficiency, no odor and the like, and can recover sulfur. However, because the biological desulfurization reaction speed is slow, the process is not easy to control, the condition requirement is strict, and the desulfurization efficiency is reduced due to unknown reasons in the frequent operation process, the large-scale industrial application of the biological desulfurization is hindered.
Dry desulfurization can be classified into chemical adsorption, chemical absorption and catalytic oxidation, and the aim of removing hydrogen sulfide is achieved mainly by oxidizing hydrogen sulfide into sulfur-containing oxide with solid desulfurizers such as iron oxide and activated carbon. Dry desulfurization is generally used for biogas having a low hydrogen sulfide content, and if the content of hydrogen sulfide gas is high, the desulfurizing agent rapidly loses efficacy, so that the desulfurization efficiency is rapidly reduced, and in addition, superheated steam with the temperature of over 400 ℃ is required for activated carbon regeneration, and when the tower diameter of a desulfurization tower is large or a material layer is high, the regeneration is incomplete. The regeneration of the ferric oxide needs oxygen, explosion can occur if the operation is not proper in the methane environment, the danger is high, and the regeneration speed of the ferric oxide is slow.
The wet oxidation desulfurization method is a chemical reaction desulfurization method, and comprises an ammonia water liquid phase catalysis method, a sizing method, a KCA method, a complex iron method and the like, wherein the complex iron method is most concerned, the wet oxidation desulfurization method not only has excellent catalytic oxidation capability, but also has low price, and on the whole, the wet desulfurization method has the problems of waste water treatment in the prior art, low desulfurization efficiency, easy loss of a catalyst and low utilization rate.
Disclosure of Invention
In view of the above, the present invention provides a biogas desulfurization method.
The invention also provides a biogas desulfurization device.
In order to solve the technical problems, the invention adopts the following technical scheme:
the biogas desulfurization method provided by the embodiment of the invention comprises the following steps:
s1, fully mixing the biogas and the desulfurization solution to enable the biogas to be micro-foamed and then carrying out desulfurization treatment reaction;
s2, carrying out gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurized liquid to obtain desulfurized biogas and a sulfur-containing desulfurized liquid;
s3, drying and purifying the obtained desulfurized biogas;
and S4, performing desulfurization regeneration treatment on the obtained sulfur-containing desulfurization solution under the action of a metal phthalocyanine catalyst and oxygen, and separating the regenerated sulfur-containing desulfurization solution for recycling.
Further, in step S1, the desulfurization solution includes sodium carbonate or a mixture of sodium carbonate and sodium bicarbonate.
Further, the step S4 includes the following steps:
s41, adding the sulfur-containing desulfurization solution into a regeneration device filled with a metal phthalocyanine catalyst, and introducing oxygen into the regeneration device for desulfurization regeneration treatment to generate elemental sulfur;
and S42, separating the generated elemental sulfur from the regenerated sulfur-containing desulfurization solution to respectively obtain elemental sulfur and a desulfurization-treated solution, and recycling the desulfurization-treated solution as the desulfurization solution.
Further, in the step S4, the metal phthalocyanine catalyst is a cobalt phthalocyanine catalyst supported on a titanium metal foam.
Further, the method of supporting the cobalt phthalocyanine catalyst on a titanium metal foam comprises the steps of:
preparing glacial acetic acid and ethanol solution, respectively adding cobalt phthalocyanine and N-dimethylformamide into the solution, stirring and dissolving, slowly adding sodium hydroxide solution until the raw materials are completely dissolved, and adding titanium metal foam into the mixed solution;
carrying out ultrasonic treatment on the solution filled with the titanium metal foam, and then placing the solution in a hydrothermal reaction kettle to react for 4 hours at the temperature of 250 ℃ to obtain the treated titanium metal foam;
and taking out the treated titanium metal foam, and drying and sintering the titanium metal foam to obtain the cobalt phthalocyanine catalyst loaded on the titanium metal foam.
Further, in the method of supporting the cobalt phthalocyanine catalyst on the titanium metal foam, the mass ratio of the glacial acetic acid, ethanol, cobalt phthalocyanine, N-dimethylformamide and titanium metal foam is 5: 30: 1: 2.5: 4.
further, when sintering the treated titanium metal foam, the treated titanium metal foam is sintered for 1 hour at the temperature of 260 ℃ and then sintered for 2 hours at the temperature of 350 ℃.
According to the methane desulfurization method provided by the embodiment of the invention, through the processes and steps, methane is subjected to micro-foaming, the desulfurization efficiency is effectively improved, the cobalt phthalocyanine catalyst loaded on titanium metal foam can reduce the loss of the catalyst and improve the utilization rate of the catalyst, and meanwhile, the foam type carrier has a large surface area, the reaction contact area is increased, and the regeneration of desulfurization solution is facilitated.
The biogas desulfurization device according to the embodiment of the invention comprises:
the gas-liquid mixing device is respectively provided with a feed inlet for adding methane and desulfurization liquid and a discharge outlet for discharging mixed liquid of the methane and the desulfurization liquid, and is used for mixing the added methane and the desulfurization liquid and slightly foaming the methane;
the inlet of the reactor is communicated with the discharge hole of the gas-liquid mixing device so as to add the mixed liquid in the gas-liquid mixing device into the reactor and carry out desulfurization reaction;
the gas-liquid separation tank is communicated with the reactor so as to transfer the mixed liquid after reaction in the reactor into the gas-liquid separation tank for gas-liquid separation and obtain desulfurized biogas and sulfur-containing desulfurized liquid;
the drying and purifying device is communicated with the gas-liquid separation tank and is used for containing and drying and purifying the desulfurized biogas separated from the gas-liquid separation tank;
and the regeneration device is respectively communicated with the gas-liquid mixing device and the gas-liquid separation tank and is used for regenerating the sulfur-containing desulfurization solution separated from the gas-liquid separation tank, separating the elemental sulfur generated in the regeneration to obtain the desulfurized liquid, and transferring the desulfurized liquid into the gas-liquid mixing device to be used as the desulfurization liquid to be mixed with the biogas.
Further, the gas-liquid mixing device is a gas-liquid mixing pump, and the reactor is a baffle reactor.
Furthermore, the regeneration device is provided with titanium metal foam loaded with metal phthalocyanine catalyst.
Furthermore, the bottom of the regeneration device is conical, a sulfur outlet for discharging the generated elemental sulfur is formed in the bottom, and a switch valve is arranged on the sulfur outlet and controls the opening and closing of the sulfur outlet through the switch valve.
Further, the biogas desulfurization device further comprises:
a bubbler arranged in the regeneration device for introducing air or oxygen into the sulfur-containing desulfurization solution.
Further, the biogas desulfurization device further comprises:
the biogas storage tank is communicated with the gas-liquid mixing device and is used for storing the biogas and adding the biogas into the gas-liquid mixing device;
and the desulfurization solution storage tank is respectively communicated with the gas-liquid mixing device and the regeneration device and is used for storing the desulfurization-treated solution obtained after regeneration in the regeneration device and adding the desulfurization-treated solution into the gas-liquid mixing device to be used as desulfurization solution to be mixed with the biogas.
Further, the biogas desulfurization device further comprises:
the device comprises at least two valves and two flow meters, wherein at least one valve and one flow meter are arranged between the biogas storage tank and the gas-liquid mixing device and are used for adjusting the flow of biogas entering the gas-liquid mixing device, and at least one valve and one flow meter are arranged between the doctor solution storage tank and the gas-liquid mixing device and are used for adjusting the flow of doctor solution.
Further, the biogas desulfurization device further comprises:
the circulating pump is respectively connected with the gas-liquid separation tank and the regeneration device and is used for pumping the sulfur-containing desulfurization solution in the gas-liquid separation tank into the regeneration device;
and the regulating valve is arranged between the circulating pump and the gas-liquid separation tank and is used for regulating the flow of the sulfur-containing desulfurization liquid in the gas-liquid separation tank into the regeneration device.
The technical scheme of the invention has the following beneficial effects:
according to the methane desulfurization device provided by the embodiment of the invention, methane can be micro-foamed, the desulfurization efficiency is improved, the cobalt phthalocyanine catalyst loaded on titanium metal foam can reduce the loss of the catalyst, the utilization rate of the catalyst is improved, the reaction contact area is increased, the regeneration of desulfurization solution is facilitated, and the regeneration efficiency is improved.
Drawings
FIG. 1 is a schematic flow diagram of a biogas desulfurization process according to one embodiment of the present invention;
fig. 2 is a schematic connection diagram of a biogas desulfurization apparatus according to an embodiment of the present invention.
Reference numerals:
a biogas desulfurization device 100;
a gas-liquid mixing device 10;
a reactor 20;
a gas-liquid separation tank 30;
a drying and purifying device 40;
a regeneration device 50; titanium metal foam 51; a bubbler 52; the on-off valve 53;
a biogas storage tank 60; a valve 61; a flow meter 62;
a desulfurization solution storage tank 70;
a circulation pump 80; the valve 81 is adjusted.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
The biogas desulfurization method according to an embodiment of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the biogas desulfurization method according to the embodiment of the present invention includes the following steps:
and step S1, fully mixing the marsh gas and the desulfurization solution to ensure that the marsh gas is micro-foamed and then carrying out desulfurization treatment reaction.
In the step, firstly, the component content in the biogas, the type and content of sulfur-containing substances such as hydrogen sulfide and sulfur-containing organic matters, the physical characteristics such as the temperature of the biogas and the like are analyzed and detected, the desulfurizing agent in the desulfurizing liquid can contain sodium carbonate, a proper amount of sodium carbonate can be added into the desulfurizing liquid according to the content of hydrogen sulfide gas in the biogas to prepare a sodium carbonate solution with a certain concentration, the concentration of the sodium carbonate in the desulfurizing liquid can be measured at intervals in the process of desulfurizing the desulfurizing liquid, and if the concentration of the sodium carbonate is lower, the reaction can be continued after the sodium carbonate is added.
The desulfurization solution can also contain a mixture of sodium carbonate and sodium bicarbonate, the content of the sodium carbonate and the sodium bicarbonate can be reasonably selected, ammonia water, quick lime and the like can also be added according to needs, the content of the ammonia water, the quick lime, the sodium carbonate and the sodium bicarbonate of the desulfurizing agent in the desulfurization solution can be adjusted according to the content of sulfur in the methane, the temperature and the pH value of the desulfurization solution can be adjusted, the temperature of the desulfurization solution can be selected from 30-70 ℃, the desulfurization reaction is facilitated, the desulfurization reaction process is easy to carry out, the mixing proportion of the methane and the desulfurizing agent is adjusted according to the content of sulfur in the methane and the type and proportion of the desulfurizing agent, the methane and the desulfurization solution are fully mixed, and the methane is enabled to be micro-foamed. When sodium carbonate and sodium bicarbonate are included in the desulfurization solution, the main reactions of the whole desulfurization process are as follows:
removing H2The chemical absorption reaction of S is shown in the following reaction formula (1):
H2S+Na2CO3→NaHS+NaHCO3 (1)
the chemical absorption reaction for removing organic sulfur is shown in the following reaction formula (2):
COS+2Na2CO3+H2O→Na2CO2S+2NaHCO3 (2)
can realize marsh gas and microbubble through the stirring, also can make marsh gas microbubble through the gas-liquid mixing pump, increase reaction area of contact does benefit to the reaction and goes on, detects the content of sulphur in marsh gas after the desulfurization reaction of a certain time, accomplishes the desulfurization reaction after meeting the requirements, increases the gas-liquid area of contact of desulfurization reaction system through making marsh gas microbubble, improves desulfurization efficiency and desulfurization effect.
And step S2, performing gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurization liquid to obtain desulfurized biogas and sulfur-containing desulfurization liquid.
In the step, after the desulfurization treatment of the desulfurization solution in step S1 is performed to react the biogas to meet the requirement, the desulfurization reaction is stopped, the mixture of the micro-foamed biogas and the desulfurization solution is subjected to gas-liquid separation to obtain the desulfurized biogas and the sulfur-containing desulfurization solution, the mixture of the micro-foamed biogas and the desulfurization solution after reaction can be transferred to a separation device, the mixed solution can be vacuumized during the gas-liquid separation process to reduce the pressure of a container for containing the mixed solution, and the stirring can be increased to accelerate the separation of the desulfurized biogas from the sulfur-containing desulfurization solution, and the desulfurized biogas and the sulfur-containing desulfurization solution obtained after separation can be transferred to corresponding storage devices respectively for subsequent drying and purification treatment of the desulfurized biogas and regeneration treatment of the sulfur-containing desulfurization solution.
And step S3, drying and purifying the obtained desulfurized biogas.
In the step, the obtained desulfurized biogas is dried and purified, the desulfurized biogas can be transferred into a drying device for drying treatment to remove water and the like in the desulfurized biogas, the dried desulfurized biogas can be transferred into a purification and absorption device, a small amount of impurities remained in the desulfurized biogas are further removed through an adsorbent, and the cleanliness of the biogas is improved.
And step S4, performing desulfurization regeneration treatment on the obtained sulfur-containing desulfurization solution under the action of a metal phthalocyanine catalyst and oxygen, and separating the regenerated sulfur-containing desulfurization solution for recycling.
In the step, the separated sulfur-containing desulfurization solution can be placed in a reactor, a metal phthalocyanine catalyst can be added into the reactor, the metal phthalocyanine catalyst can be metal phthalocyanine compounds such as metal zinc phthalocyanine, metal iron phthalocyanine, metal nickel phthalocyanine and the like, the metal phthalocyanine catalyst can be a cobalt phthalocyanine catalyst loaded on titanium metal foam, the metal phthalocyanine catalyst can be loaded on carrier foam, the reaction contact area of the catalyst and the sulfur-containing desulfurization solution is increased, meanwhile, oxygen or air is introduced into the sulfur-containing desulfurization solution, desulfurization regeneration treatment is carried out under the action of the metal phthalocyanine catalyst and the oxygen, under the action of the metal phthalocyanine catalyst, the oxygen and the sulfur-containing desulfurization solution react to generate a sulfur simple substance, standing and precipitating after reacting for a certain time, the sulfur precipitates to the bottom of the reactor, the sulfur simple substance can be separated from an opening at the bottom of the reactor, the regenerated desulfurization solution can flow back to a desulfurization solution storage tank to be continuously mixed with biogas for recycling, the usage amount of the desulfurization solution is reduced, and the utilization rate of the desulfurization solution is improved.
In the steps and the process, the methane is subjected to micro-foaming, the reaction contact area is increased, the desulfurization efficiency is effectively improved, and the sulfur-containing desulfurization solution is subjected to desulfurization regeneration treatment under the action of the metal phthalocyanine catalyst and oxygen, so that the sulfur in the sulfur-containing desulfurization solution can be effectively removed, and the regeneration of the desulfurization solution is facilitated.
According to an embodiment of the present invention, in step S1, the desulfurization solution may include sodium carbonate or a mixture of sodium carbonate and sodium bicarbonate, the content of the sodium carbonate may be reasonably selected according to actual conditions, the mass fraction of the sodium carbonate may be between 3% and 15%, the desulfurization solution may also include both sodium carbonate and sodium bicarbonate, the mass fraction of the sodium bicarbonate may be between 2% and 9%, and the proportion and content of the sodium carbonate and the sodium bicarbonate may also be reasonably selected according to needs.
In some embodiments of the present invention, step S4 may include the steps of:
step S41, adding the sulfur-containing desulfurization solution into a regenerating device filled with a metal phthalocyanine catalyst, and introducing oxygen into the regenerating device for desulfurization regeneration treatment to generate elemental sulfur;
and step S42, separating the generated elemental sulfur from the regenerated sulfur-containing desulfurization solution to respectively obtain elemental sulfur and the desulfurization solution, and recycling the desulfurization solution as the desulfurization solution.
That is, in step S41, the sulfur-containing desulfurization solution may be added into a regeneration device containing a metal phthalocyanine catalyst, the metal phthalocyanine catalyst is placed in the sulfur-containing desulfurization solution, and air or oxygen is introduced into the sulfur-containing desulfurization solution at the same time, so as to perform desulfurization regeneration treatment under the action of the metal phthalocyanine catalyst and oxygen, the temperature of the sulfur-containing desulfurization solution may be selected from 30 ℃ to 80 ℃, which is favorable for the regeneration reaction, under the action of the metal phthalocyanine catalyst, the oxygen reacts with the sulfur-containing substances in the sulfur-containing desulfurization solution to generate elemental sulfur, and when the desulfurization solution includes sodium carbonate and sodium bicarbonate, the main reaction in the reaction process is as follows:
the catalytic oxidation sulfur evolution reaction is shown as the following formulas (3) to (6):
NaHS+(X-1)S+NaHCO3→Na2SX+CO2+H2O (3)
the sulfur-containing substance is converted into the elemental sulfur so as to be separated, the regeneration of the sulfur-containing desulfurization solution is realized, the metal phthalocyanine catalyst can be loaded on the titanium metal foam, the catalyst can be fixed by loading the catalyst on the titanium metal foam, the loss of the catalyst is reduced, the utilization rate of the catalyst is improved, the contact area of the catalyst and the sulfur-containing desulfurization solution can be increased, and the reaction efficiency is improved.
In step S42, the generated elemental sulfur is separated from the regenerated sulfur-containing desulfurization solution to obtain elemental sulfur and a desulfurization-treated solution, the elemental sulfur precipitates together after precipitation, and then the precipitated elemental sulfur and the desulfurization-treated solution can be separated, and the desulfurization-treated solution can be recycled as the desulfurization solution and can be stored in a storage tank.
According to other embodiments of the present invention, in step S4, the metal phthalocyanine catalyst may be a cobalt phthalocyanine catalyst loaded on the titanium metal foam, and the cobalt phthalocyanine catalyst is loaded on the titanium metal foam, so that the contact area between the cobalt phthalocyanine catalyst and the sulfur-containing desulfurization solution can be increased, the regeneration reaction is promoted, the regeneration rate is increased, and the cobalt phthalocyanine catalyst fixed on the titanium metal foam can reduce the loss of the catalyst and increase the utilization rate of the catalyst.
According to some embodiments of the present invention, a method of supporting a cobalt phthalocyanine catalyst on a titanium metal foam comprises the steps of:
preparing a solution by taking a proper amount of glacial acetic acid and ethanol, adding cobalt phthalocyanine into the prepared glacial acetic acid and ethanol solution, adding N-dimethylformamide, continuously stirring for dissolving, slowly adding a sodium hydroxide solution after stirring for a period of time, wherein the pH value of the sodium hydroxide solution is between 8.5 and 9.0 until the raw materials in the solution are completely dissolved, and finally adding titanium metal foam into the solution;
the solution containing the titanium metal foam is subjected to ultrasonic treatment and then placed in a hydrothermal reaction kettle to react for 4 hours at the temperature of 250 ℃ to obtain the treated titanium metal foam, the specific reaction temperature and time can also be reasonably adjusted according to the actual situation, the reaction temperature can be gradually increased in temperature, the temperature increase rate can be reasonably selected and can be 5 ℃/min, and the solution can be naturally cooled after the reaction is finished;
and taking out the treated titanium metal foam, drying and sintering, wherein the sintering temperature and time can be reasonably selected according to actual conditions, and the heating rate during sintering can be reasonably selected according to actual conditions, so that the cobalt phthalocyanine catalyst loaded on the titanium metal foam is obtained.
In some embodiments of the present invention, in the method of supporting a cobalt phthalocyanine catalyst on a titanium metal foam, a mass ratio of glacial acetic acid, ethanol, cobalt phthalocyanine, N-dimethylformamide, and titanium metal foam may be 5: 30: 1: 2.5: 4, the specific mass ratio can be reasonably adjusted according to actual conditions, and the cobalt phthalocyanine catalyst loaded on the titanium metal foam obtained in the ratio is better.
According to some embodiments of the present invention, when sintering the processed titanium metal foam, the processed titanium metal foam may be sintered at a temperature of 260 ℃ for 1 hour, and the temperature may be raised at a suitable temperature raising rate, for example, at a temperature raising rate of 5 ℃/min from room temperature to 260 ℃, and then sintered at a temperature of 350 ℃ for 2 hours, or at a temperature raising rate of 5 ℃/min to 350 ℃, and after sintering, the temperature is lowered to obtain the cobalt phthalocyanine catalyst loaded on the titanium metal foam, so that the cobalt phthalocyanine catalyst is fixed on the titanium metal foam, thereby reducing catalyst loss and increasing contact area.
According to the biogas desulfurization method provided by the embodiment of the invention, through the processes and steps, biogas is subjected to micro-foaming, the gas-liquid contact area is increased, the desulfurization efficiency is effectively improved, the cobalt phthalocyanine catalyst is loaded on titanium metal foam, the catalyst loss can be reduced, the catalyst utilization rate is improved, meanwhile, the foam type load body has a large surface area, the reaction contact area is increased, and the regeneration of desulfurization liquid is facilitated.
The biogas desulfurization method is further described below with reference to some specific examples.
Example 1
Fully mixing the biogas and the desulfurization solution to enable the biogas to be micro-foamed, and then carrying out desulfurization treatment reaction, wherein a certain mass fraction of sodium carbonate desulfurization solution can be prepared, the mass fraction of sodium carbonate in the desulfurization solution can be 6%, the temperature of the desulfurization solution can be 30 ℃, the concentration of sodium carbonate in the desulfurization solution can be measured at regular intervals, for example, the interval can be 15min, if the concentration of sodium carbonate is low, the reaction can be temporarily carried out, and the reaction can be continued after sodium carbonate is added; carrying out gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurization liquid to obtain desulfurized biogas and a sulfur-containing desulfurization liquid; drying and purifying the obtained desulfurized biogas by a drying device; adding a cobalt phthalocyanine catalyst loaded on titanium metal foam into the obtained sulfur-containing desulfurization solution, introducing oxygen into the sulfur-containing desulfurization solution, controlling the temperature of the sulfur-containing desulfurization solution to be 40 ℃, performing desulfurization regeneration treatment under the action of the catalyst and the oxygen to generate elemental sulfur, separating the generated elemental sulfur from the regenerated sulfur-containing desulfurization solution to respectively obtain elemental sulfur and a desulfurization-treated solution, and recycling the desulfurization-treated solution as the desulfurization solution. The preparation method of the cobalt phthalocyanine catalyst loaded on the titanium metal foam in the embodiment is as follows:
preparing a mixed solution by taking 5 parts (by mass) of glacial acetic acid and 30 parts of ethanol, weighing 1 part of cobalt phthalocyanine, adding the cobalt phthalocyanine into the mixed solution, adding 2.5 parts of N-dimethylformamide, continuously stirring for 20min, slowly adding a sodium hydroxide solution (the pH value is 8.5-9.0) until the raw materials are completely dissolved, finally adding 4 parts of titanium metal foam, soaking the titanium metal foam into the mixed solution, carrying out ultrasonic treatment for 20min, transferring the mixture into a hydrothermal reaction kettle, heating to 250 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation for 4h, and naturally cooling. And taking out the treated titanium metal foam, drying and sintering, heating to 260 ℃ from room temperature at the heating rate of 5 ℃/min, sintering for 1h, heating to 350 ℃ at the heating rate of 5 ℃/min, sintering for 2h, and naturally cooling to obtain the cobalt phthalocyanine catalyst loaded on the titanium metal foam.
According to the biogas desulfurization method provided by the embodiment of the invention, through the processes and steps, biogas is subjected to micro-foaming, the gas-liquid contact area is increased, the desulfurization efficiency is effectively improved, the prepared cobalt phthalocyanine catalyst loaded on titanium metal foam can reduce the loss of the catalyst and improve the utilization rate of the catalyst, and meanwhile, the foam type load body has a large surface area, the reaction contact area is increased, and the regeneration of desulfurization solution is facilitated.
Example 2
Fully mixing the biogas and the desulfurization solution to enable the biogas to be micro-foamed, and then carrying out desulfurization treatment reaction, wherein a certain mass fraction of sodium carbonate desulfurization solution can be prepared, the mass fraction of sodium carbonate in the desulfurization solution can be 6%, the temperature of the desulfurization solution can be 45 ℃, the concentration of sodium carbonate in the desulfurization solution can be measured at regular intervals, for example, 20min can be carried out, if the concentration of sodium carbonate is low, the reaction can be temporarily carried out, and the reaction can be continued after sodium carbonate is added; carrying out gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurization liquid to obtain desulfurized biogas and a sulfur-containing desulfurization liquid; drying and purifying the obtained desulfurized biogas by a drying device; adding a cobalt phthalocyanine catalyst loaded on titanium metal foam into the obtained sulfur-containing desulfurization solution, introducing oxygen into the sulfur-containing desulfurization solution, controlling the temperature of the sulfur-containing desulfurization solution to be 50 ℃, performing desulfurization regeneration treatment under the action of the catalyst and the oxygen to generate elemental sulfur, separating the generated elemental sulfur from the regenerated sulfur-containing desulfurization solution to respectively obtain elemental sulfur and a desulfurization-treated solution, and recycling the desulfurization-treated solution as the desulfurization solution. The preparation method of the cobalt phthalocyanine catalyst loaded on the titanium metal foam in the embodiment is as follows:
preparing a mixed solution by taking 5 parts (by mass) of glacial acetic acid and 30 parts of ethanol, weighing 1 part of cobalt phthalocyanine, adding the cobalt phthalocyanine into the mixed solution, adding 2.5 parts of N-dimethylformamide, continuously stirring for 20min, slowly adding a sodium hydroxide solution (the pH value is 8.5-9.0) until the raw materials are completely dissolved, finally adding 4 parts of titanium metal foam, soaking the titanium metal foam into the mixed solution, carrying out ultrasonic treatment for 20min, transferring the mixture into a hydrothermal reaction kettle, heating to 250 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation for 4h, and naturally cooling. And taking out the treated titanium metal foam, drying and sintering, heating to 260 ℃ from room temperature at the heating rate of 5 ℃/min, sintering for 1h, heating to 350 ℃ at the heating rate of 5 ℃/min, sintering for 2h, and naturally cooling to obtain the cobalt phthalocyanine catalyst loaded on the titanium metal foam.
According to the biogas desulfurization method provided by the embodiment of the invention, through the processes and steps, biogas is subjected to micro-foaming, the gas-liquid contact area is increased, the desulfurization efficiency is effectively improved, the prepared cobalt phthalocyanine catalyst loaded on titanium metal foam can be used for reducing the loss of the catalyst, the reaction contact area is increased, and the regeneration of desulfurization solution is facilitated.
Example 3
Fully mixing the biogas and the desulfurization solution to enable the biogas to be micro-foamed, and then carrying out desulfurization treatment reaction, wherein the desulfurization solution of sodium carbonate and sodium bicarbonate with a certain mass fraction can be prepared, the mass fraction of sodium carbonate in the desulfurization solution can be 6%, the mass fraction of sodium bicarbonate can be 3%, the temperature of the desulfurization solution can be 60 ℃, the concentrations of sodium carbonate and sodium bicarbonate in the desulfurization solution can be measured at intervals of 15min, if the concentration of sodium carbonate or sodium bicarbonate is low, the reaction can be tentatively carried out, and the reaction is continued after the sodium carbonate or sodium bicarbonate is added; carrying out gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurization liquid to obtain desulfurized biogas and a sulfur-containing desulfurization liquid; drying and purifying the obtained desulfurized biogas by a drying device; adding a cobalt phthalocyanine catalyst loaded on titanium metal foam into the obtained sulfur-containing desulfurization solution, introducing oxygen into the sulfur-containing desulfurization solution, controlling the temperature of the sulfur-containing desulfurization solution to be 55 ℃, performing desulfurization regeneration treatment under the action of the catalyst and the oxygen to generate elemental sulfur, separating the generated elemental sulfur from the regenerated sulfur-containing desulfurization solution to respectively obtain elemental sulfur and a desulfurization-treated solution, and recycling the desulfurization-treated solution as the desulfurization solution. The preparation method of the cobalt phthalocyanine catalyst loaded on the titanium metal foam in the embodiment is as follows:
preparing a mixed solution by taking 5 parts (by mass) of glacial acetic acid and 30 parts of ethanol, weighing 1 part of cobalt phthalocyanine, adding the cobalt phthalocyanine into the mixed solution, adding 2.5 parts of N-dimethylformamide, continuously stirring for 20min, slowly adding a sodium hydroxide solution (the pH value is 8.5-9.0) until the raw materials are completely dissolved, finally adding 4 parts of titanium metal foam, soaking the titanium metal foam into the mixed solution, carrying out ultrasonic treatment for 20min, transferring the mixture into a hydrothermal reaction kettle, heating to 250 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation for 4h, and naturally cooling. And taking out the treated titanium metal foam, drying and sintering, heating to 260 ℃ from room temperature at the heating rate of 5 ℃/min, sintering for 1h, heating to 350 ℃ at the heating rate of 5 ℃/min, sintering for 2h, and naturally cooling to obtain the cobalt phthalocyanine catalyst loaded on the titanium metal foam.
According to the biogas desulfurization method provided by the embodiment of the invention, through the processes and steps, biogas is subjected to micro-foaming, the gas-liquid contact area is increased, the desulfurization efficiency is improved, the loss of the catalyst can be reduced by using the prepared cobalt phthalocyanine catalyst loaded on titanium metal foam, the reaction contact area is increased, and the regeneration rate of the desulfurization solution is accelerated.
Example 4
Fully mixing biogas and a desulfurization solution to enable the biogas to be micro-foamed, then carrying out desulfurization treatment reaction, firstly preparing the desulfurization solution of sodium carbonate and sodium bicarbonate with a certain mass fraction, wherein the mass fraction of sodium carbonate in the desulfurization solution can be 9%, the mass fraction of sodium bicarbonate can be 3%, the temperature of the desulfurization solution can be 70 ℃, the concentration of sodium carbonate and sodium bicarbonate in the desulfurization solution can be measured at intervals of 15min, if the concentration of sodium carbonate or sodium bicarbonate is low, the reaction can be tentatively carried out, and the reaction is continued after the sodium carbonate or sodium bicarbonate is added; carrying out gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurization liquid to obtain desulfurized biogas and a sulfur-containing desulfurization liquid; drying and purifying the obtained desulfurized biogas by a drying device; adding a cobalt phthalocyanine catalyst loaded on titanium metal foam into the obtained sulfur-containing desulfurization solution, introducing oxygen into the sulfur-containing desulfurization solution, controlling the temperature of the sulfur-containing desulfurization solution to be 72 ℃, performing desulfurization regeneration treatment under the action of the catalyst and the oxygen to generate elemental sulfur, separating the generated elemental sulfur from the regenerated sulfur-containing desulfurization solution to respectively obtain elemental sulfur and a desulfurization-treated solution, and recycling the desulfurization-treated solution as the desulfurization solution. The preparation method of the cobalt phthalocyanine catalyst loaded on the titanium metal foam in the embodiment is as follows:
preparing a mixed solution by taking 5 parts (by mass) of glacial acetic acid and 30 parts of ethanol, weighing 1 part of cobalt phthalocyanine, adding the cobalt phthalocyanine into the mixed solution, adding 2.5 parts of N-dimethylformamide, continuously stirring for 20min, slowly adding a sodium hydroxide solution (the pH value is 8.5-9.0) until the raw materials are completely dissolved, finally adding 4 parts of titanium metal foam, soaking the titanium metal foam into the mixed solution, carrying out ultrasonic treatment for 20min, transferring the mixture into a hydrothermal reaction kettle, heating to 250 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation for 4h, and naturally cooling. And taking out the treated titanium metal foam, drying and sintering, heating to 260 ℃ from room temperature at the heating rate of 5 ℃/min, sintering for 1h, heating to 350 ℃ at the heating rate of 5 ℃/min, sintering for 2h, and naturally cooling to obtain the cobalt phthalocyanine catalyst loaded on the titanium metal foam.
According to the biogas desulfurization method provided by the embodiment of the invention, through the processes and steps, biogas is subjected to micro-foaming, the gas-liquid contact area is increased, the desulfurization efficiency is improved, the loss of the catalyst can be reduced by using the prepared cobalt phthalocyanine catalyst loaded on titanium metal foam, the reaction contact area is increased, and the regeneration rate of the desulfurization solution is accelerated.
Example 5
Fully mixing biogas and a desulfurization solution to enable the biogas to be micro-foamed, then carrying out desulfurization treatment reaction, firstly preparing the desulfurization solution containing sodium carbonate and sodium bicarbonate, wherein the mass fraction of sodium carbonate in the desulfurization solution can be 7%, the mass fraction of sodium bicarbonate can be 2%, the temperature of the desulfurization solution can be 70 ℃, the concentrations of sodium carbonate and sodium bicarbonate in the desulfurization solution are measured at intervals of 30min, if the concentration of sodium carbonate or sodium bicarbonate is low, the reaction can be tentatively carried out, and the reaction is continuously carried out after the sodium carbonate or sodium bicarbonate is added; carrying out gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurization liquid to obtain desulfurized biogas and a sulfur-containing desulfurization liquid; drying and purifying the obtained desulfurized biogas by a drying device; adding a cobalt phthalocyanine catalyst loaded on titanium metal foam into the obtained sulfur-containing desulfurization solution, introducing oxygen into the sulfur-containing desulfurization solution, controlling the temperature of the sulfur-containing desulfurization solution to be 67 ℃, performing desulfurization regeneration treatment under the action of the catalyst and the oxygen to generate elemental sulfur, separating the generated elemental sulfur from the regenerated sulfur-containing desulfurization solution to respectively obtain elemental sulfur and a desulfurization-treated solution, and recycling the desulfurization-treated solution as the desulfurization solution. The preparation method of the cobalt phthalocyanine catalyst loaded on the titanium metal foam in the embodiment is as follows:
preparing a mixed solution by taking 5 parts (by mass) of glacial acetic acid and 30 parts of ethanol, weighing 1 part of cobalt phthalocyanine, adding the cobalt phthalocyanine into the mixed solution, adding 2.5 parts of N-dimethylformamide, continuously stirring for 20min, slowly adding a sodium hydroxide solution (the pH value is 8.5-9.0) until the raw materials are completely dissolved, finally adding 4 parts of titanium metal foam, soaking the titanium metal foam into the mixed solution, carrying out ultrasonic treatment for 20min, transferring the mixture into a hydrothermal reaction kettle, heating to 250 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation for 4h, and naturally cooling. And taking out the treated titanium metal foam, drying and sintering, heating to 260 ℃ from room temperature at the heating rate of 5 ℃/min, sintering for 1h, heating to 350 ℃ at the heating rate of 5 ℃/min, sintering for 2h, and naturally cooling to obtain the cobalt phthalocyanine catalyst loaded on the titanium metal foam.
According to the biogas desulfurization method provided by the embodiment of the invention, through the processes and steps, biogas is subjected to micro-foaming, the gas-liquid contact area is increased, the desulfurization efficiency is improved, the loss of the catalyst can be reduced by using the prepared cobalt phthalocyanine catalyst loaded on titanium metal foam, the reaction contact area is increased, and the regeneration rate of the desulfurization solution is accelerated.
According to the methane desulfurization method provided by the embodiment of the invention, methane is micro-foamed through the process and the steps, the gas-liquid contact area is increased, the desulfurization efficiency is effectively improved, the loss of the catalyst can be reduced and the utilization rate of the catalyst is improved by using the prepared cobalt phthalocyanine catalyst loaded on the titanium metal foam, and meanwhile, the foam type carrier has a large surface area, the reaction contact area is increased, and the regeneration of the desulfurization solution is facilitated.
The invention also provides a biogas desulfurization device 100.
As shown in fig. 2, the biogas desulfurization apparatus 100 includes a gas-liquid mixing device 10, a reactor 20, a gas-liquid separation tank 30, a drying and purifying device 40, and a regeneration device 50.
Specifically, the gas-liquid mixing device 10 is respectively provided with a feed inlet for feeding the biogas and the desulfurization solution and a discharge outlet for discharging the mixed solution of the biogas and the desulfurization solution, and the gas-liquid mixing device 10 is used for mixing the fed biogas and the desulfurization solution and slightly foaming the biogas; an inlet of the reactor 20 is communicated with a discharge hole of the gas-liquid mixing device 10 so as to add the mixed liquid in the gas-liquid mixing device 10 into the reactor 20 and carry out desulfurization reaction; the gas-liquid separation tank 30 is communicated with the reactor 20 so as to transfer the mixed liquid after reaction in the reactor 20 into the gas-liquid separation tank 30 for gas-liquid separation and obtain desulfurized biogas and sulfur-containing desulfurized liquid; the drying and purifying device 40 is connected with the gas-liquid separation tank 30 and is used for containing and drying and purifying the desulfurized biogas separated from the gas-liquid separation tank 30; the regeneration device 50 is respectively communicated with the gas-liquid mixing device 10 and the gas-liquid separation tank 30, and is used for regenerating the sulfur-containing desulfurization solution separated from the gas-liquid separation tank 30, separating the elemental sulfur generated in the regeneration to obtain the desulfurization treated solution, and transferring the desulfurization treated solution into the gas-liquid mixing device 10 to be used as the desulfurization solution to be mixed with the biogas.
That is to say, the biogas desulfurization device 100 is mainly composed of a gas-liquid mixing device 10, a reactor 20, a gas-liquid separation tank 30, a drying and purifying device 40 and a regenerating device 50, wherein a feed port and a discharge port can be respectively arranged on the gas-liquid mixing device 10, the specific positions can be reasonably selected, the gas-liquid mixing device 10 can be arranged at the bottom of the gas-liquid mixing device 10, the gas-liquid mixing device 10 can be a gas-liquid mixing pump, the gas-liquid mixing pump can be a container with a stirring device, the feed port can be used for adding biogas and desulfurization liquid, the discharge port can be used for discharging mixed liquid of the biogas and the desulfurization liquid, the gas-liquid mixing device 10 can be used for mixing the added biogas and the desulfurization liquid, the biogas can be micro-foamed through the gas-liquid mixing device 10, the contact area of the micro-foamed biogas and the desulfurization liquid. The gas-liquid mixing device 10 can be connected with the reactor 20, the inlet of the reactor 20 can be communicated with the discharge hole of the gas-liquid mixing device 10, the mixture of the methane micro-bubbled in the gas-liquid mixing device 10 and the desulfurization solution can be transferred into the reactor 20, the mixture is subjected to desulfurization reaction in the reactor 20, and the desulfurization can be stopped when the sulfur-containing substances in the methane are completely removed.
The gas-liquid separation tank 30 can be communicated with the reactor 20, after the mixture of the micro-bubble methane and the desulfurization solution is desulfurized, the mixture reacted in the reactor 20 can be transferred into the gas-liquid separation tank 30 for gas-liquid separation to obtain the desulfurized methane and the sulfur-containing desulfurization solution, then the desulfurized methane and the sulfur-containing desulfurization solution can be respectively treated, the desulfurized methane can be dried and purified, and the sulfur-containing desulfurization solution can be regenerated. The drying and purifying device 40 can be communicated with the gas-liquid separation tank 30, the desulfurized biogas obtained after separation can be transferred into the drying and purifying device 40, the drying and purifying device 40 can be used for containing and drying and purifying the desulfurized biogas separated from the gas-liquid separation tank 30, and the type and size of the drying and purifying device 40 can be reasonably selected according to the drying and purifying amount of the desulfurized biogas.
The regeneration device 50 may be respectively communicated with the gas-liquid mixing device 10 and the gas-liquid separation tank 30, a device capable of introducing air or oxygen may be disposed in the regeneration device 50, a catalyst such as a metal phthalocyanine catalyst may be disposed, the catalyst may be supported on a foam, the sulfur-containing desulfurization solution separated in the gas-liquid separation tank 30 may be transferred to the regeneration device 50, the regeneration device 50 may be configured to regenerate the sulfur-containing desulfurization solution separated in the gas-liquid separation tank 30, elemental sulfur may be generated after the regeneration treatment of the sulfur-containing desulfurization solution, the generated elemental sulfur may be separated from the regeneration device 50 to obtain a desulfurization treatment solution in the regeneration device 50, the desulfurization treatment solution may be transferred to the gas-liquid mixing device 10, the desulfurization treatment solution may be further mixed with biogas in the gas-liquid mixing device 10 as the desulfurization solution, so as to realize recycling of the desulfurization solution, the utilization rate of the desulfurization solution is improved.
Therefore, according to the methane desulfurization device 100 of the embodiment of the present invention, the methane can be micro-foamed, the contact area between the methane and the desulfurization solution can be increased, the desulfurization efficiency can be improved, the regeneration device 50 can regenerate the sulfur-containing desulfurization solution, the cyclic utilization of the desulfurization solution can be realized, and the device is simple in structure and easy to realize through the utilization rate of the desulfurization solution.
In an embodiment of the present invention, the gas-liquid mixing device 10 may be a gas-liquid mixing pump, the gas-liquid mixing pump sucks in the biogas and the desulfurization solution at the same time through negative pressure, the biogas and the desulfurization solution are fully mixed under the high-speed rotation of the pump impeller, meanwhile, the micro-bubbling of the biogas is realized, the gas-liquid contact area of a reaction system of the biogas and the desulfurization solution is increased, the desulfurization reaction speed is increased, and the desulfurization efficiency is improved.
In another embodiment of the present invention, the reactor 20 may be a baffled reactor, and the baffled reactor may disturb the micro-bubbled biogas and desulfurization solution in the reactor 20 to promote the desulfurization reaction.
In some embodiments of the present invention, the regeneration device 50 may be provided with titanium metal foams 51 loaded with a metal phthalocyanine catalyst, and the titanium metal foams 51 may be respectively disposed at the bottom and the middle of the regeneration device 50, so that the titanium metal foams 51 may be disposed in the sulfur-containing desulfurization solution, and the titanium metal foams 51 may increase a contact area between the catalyst and the sulfur-containing desulfurization solution in the regeneration device 50, so that the metal phthalocyanine catalyst may have a better promoting effect on the regeneration reaction, and the metal phthalocyanine catalyst is fixed on the titanium metal foams 51, which may reduce the loss of the catalyst and improve the utilization rate of the catalyst.
In other embodiments of the present invention, the bottom of the regeneration device 50 may be conical, and a sulfur outlet for discharging the generated elemental sulfur may be disposed at the bottom, so as to facilitate the separation and discharge of the elemental sulfur, and a switch valve 53 may be disposed at the sulfur outlet, and the switch of the sulfur outlet is controlled by the switch valve 53, so as to facilitate the discharge and separation of the elemental sulfur.
According to some embodiments of the present invention, the biogas desulfurization apparatus 100 may further include a bubbler 52, and the bubbler 52 may be disposed at a suitable position in the regeneration apparatus 50, and may be disposed at the bottom of the bubbler 52, so that the bubbler 52 may introduce air or oxygen into the sulfur-containing desulfurization solution, and when the bubbler 52 introduces air or oxygen into the sulfur-containing desulfurization solution, the air or oxygen may rise in the sulfur-containing desulfurization solution, so as to facilitate the oxygen to participate in the regeneration reaction.
According to other embodiments of the present invention, the biogas desulfurization apparatus 100 may further include a biogas storage tank 60 and a desulfurization solution storage tank 70, wherein the biogas storage tank 60 may be in communication with the gas-liquid mixing apparatus 10, the biogas storage tank 60 may be used to store biogas, the biogas may be added into the gas-liquid mixing apparatus 10 when the gas-liquid mixing apparatus 10 is opened, or a buffer pressure stabilizer may be installed between the biogas storage tank 60 and the gas-liquid mixing apparatus 10, for example, the buffer pressure stabilizer may be a pressure reducing valve, or a buffer tank, so that the biogas can stably enter the gas-liquid mixing apparatus 10.
The desulfurization liquid storage tank 70 can be respectively communicated with the gas-liquid mixing device 10 and the regeneration device 50 and is used for storing the desulfurization treatment liquid obtained after regeneration and separation in the regeneration device 50 and adding the desulfurization treatment liquid into the gas-liquid mixing device 10 to be mixed with biogas as desulfurization liquid, so that micro-foaming of biogas is realized, a buffering and pressure stabilizing device can be arranged between the desulfurization liquid storage tank 70 and the gas-liquid mixing device 10, the buffering and pressure stabilizing device can be a pressure reducing valve and can be a buffer tank, and the desulfurization liquid can stably enter the gas-liquid mixing device 10.
In the specific implementation process of some embodiments of the present invention, the biogas desulfurization apparatus 100 may further include at least two valves 61 and two flow meters 62, at least one valve 61 and one flow meter 62 may be disposed between the biogas storage tank 60 and the gas-liquid mixing apparatus 10 for adjusting the flow rate of the biogas entering the gas-liquid mixing apparatus 10, so that the flow rate of the biogas may be displayed, and the control operation is convenient, and at least one valve 61 and one flow meter 62 may be disposed between the desulfurization solution storage tank 70 and the gas-liquid mixing apparatus 10 for adjusting the flow rate of the desulfurization solution, so that the flow rate of the desulfurization solution may be displayed, and the control operation is convenient.
In other embodiments of the present invention, the biogas desulfurization apparatus 100 may further include a circulation pump 80 and an adjustment valve 81, wherein the circulation pump 80 may be connected to the gas-liquid separation tank 30 and the regeneration apparatus 50, respectively, for pumping the sulfur-containing desulfurization solution in the gas-liquid separation tank 30 into the regeneration apparatus 50, and the adjustment valve 81 may be disposed between the circulation pump 80 and the gas-liquid separation tank 30 for adjusting the flow rate of the sulfur-containing desulfurization solution in the gas-liquid separation tank 30 into the regeneration apparatus 50.
According to the methane desulfurization device 100 provided by the embodiment of the invention, methane can be micro-foamed, the contact area between the methane and desulfurization liquid is increased, the desulfurization efficiency is improved, the metal phthalocyanine catalyst is loaded on titanium metal foam, the catalyst loss can be reduced, the catalyst utilization rate is improved, the reaction contact area is increased, the regeneration of the desulfurization liquid is facilitated, and the regeneration efficiency is improved.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (12)
1. A biogas desulfurization method is characterized by comprising the following steps:
s1, fully mixing the biogas and the desulfurization solution to enable the biogas to be micro-foamed and then carrying out desulfurization treatment reaction;
s2, carrying out gas-liquid separation on the mixed liquid of the desulfurized biogas and the desulfurized liquid to obtain desulfurized biogas and a sulfur-containing desulfurized liquid;
s3, drying and purifying the obtained desulfurized biogas;
s4, performing desulfurization regeneration treatment on the obtained sulfur-containing desulfurization solution under the action of a metal phthalocyanine catalyst and oxygen, and recycling the regenerated sulfur-containing desulfurization solution after separation treatment; the metal phthalocyanine catalyst is a cobalt phthalocyanine catalyst loaded on titanium metal foam;
the step S4 includes the steps of:
s41, adding the sulfur-containing desulfurization solution into a regeneration device filled with a metal phthalocyanine catalyst, and introducing oxygen into the regeneration device for desulfurization regeneration treatment to generate elemental sulfur;
s42, separating the generated elemental sulfur from the regenerated sulfur-containing desulfurization solution to respectively obtain elemental sulfur and a desulfurization-treated solution, and recycling the desulfurization-treated solution as a desulfurization solution;
the biogas desulfurization device used in the biogas desulfurization method comprises:
the gas-liquid mixing device is respectively provided with a feed inlet for adding methane and desulfurization liquid and a discharge outlet for discharging mixed liquid of the methane and the desulfurization liquid, and is used for mixing the added methane and the desulfurization liquid and slightly foaming the methane;
the inlet of the reactor is communicated with the discharge hole of the gas-liquid mixing device so as to add the mixed liquid in the gas-liquid mixing device into the reactor and carry out desulfurization reaction;
the gas-liquid separation tank is communicated with the reactor so as to transfer the mixed liquid after reaction in the reactor into the gas-liquid separation tank for gas-liquid separation and obtain desulfurized biogas and sulfur-containing desulfurized liquid;
the drying and purifying device is communicated with the gas-liquid separation tank and is used for containing and drying and purifying the desulfurized biogas separated from the gas-liquid separation tank;
and the regeneration device is respectively communicated with the gas-liquid mixing device and the gas-liquid separation tank and is used for regenerating the sulfur-containing desulfurization solution separated from the gas-liquid separation tank, separating the elemental sulfur generated in the regeneration to obtain the desulfurized liquid, and transferring the desulfurized liquid into the gas-liquid mixing device to be used as the desulfurization liquid to be mixed with the biogas.
2. The biogas desulfurization method according to claim 1, wherein in the step S1, the desulfurization solution comprises sodium carbonate or a mixture of sodium carbonate and sodium bicarbonate.
3. The biogas desulfurization method according to claim 1, characterized in that the method of supporting the cobalt phthalocyanine catalyst on titanium metal foam comprises the steps of:
preparing glacial acetic acid and ethanol solution, respectively adding cobalt phthalocyanine and N-dimethylformamide into the solution, stirring and dissolving, slowly adding sodium hydroxide solution until the raw materials are completely dissolved, and adding titanium metal foam into the mixed solution;
carrying out ultrasonic treatment on the solution filled with the titanium metal foam, and then placing the solution in a hydrothermal reaction kettle to react for 4 hours at the temperature of 250 ℃ to obtain the treated titanium metal foam;
and taking out the treated titanium metal foam, and drying and sintering the titanium metal foam to obtain the cobalt phthalocyanine catalyst loaded on the titanium metal foam.
4. The biogas desulfurization method according to claim 3, wherein in the method of supporting the cobalt phthalocyanine catalyst on the titanium metal foam, the mass ratio of the glacial acetic acid, the ethanol, the cobalt phthalocyanine, the N-dimethylformamide and the titanium metal foam is 5: 30: 1: 2.5: 4.
5. the biogas desulfurization method of claim 3, wherein the treated titanium metal foam is sintered at a temperature of 260 ℃ for 1 hour, and then at a temperature of 350 ℃ for 2 hours.
6. The biogas desulfurization method of claim 1, wherein the gas-liquid mixing device is a gas-liquid mixing pump, and the reactor is a baffled reactor.
7. The biogas desulfurization method according to claim 1, wherein the regeneration device is provided with titanium metal foam loaded with a metal phthalocyanine catalyst.
8. The biogas desulfurization method according to claim 1, wherein the bottom of the regeneration device is tapered, a sulfur outlet for discharging the generated elemental sulfur is provided at the bottom, and a switch valve for controlling the opening and closing of the sulfur outlet is provided at the sulfur outlet.
9. The biogas desulfurization method according to claim 1, further comprising:
a bubbler arranged in the regeneration device for introducing air or oxygen into the sulfur-containing desulfurization solution.
10. The biogas desulfurization method according to claim 1, further comprising:
the biogas storage tank is communicated with the gas-liquid mixing device and is used for storing the biogas and adding the biogas into the gas-liquid mixing device;
and the desulfurization solution storage tank is respectively communicated with the gas-liquid mixing device and the regeneration device and is used for storing the desulfurization-treated solution obtained after regeneration in the regeneration device and adding the desulfurization-treated solution into the gas-liquid mixing device to be used as desulfurization solution to be mixed with the biogas.
11. The biogas desulfurization method according to claim 10, further comprising:
the device comprises at least two valves and two flow meters, wherein at least one valve and one flow meter are arranged between the biogas storage tank and the gas-liquid mixing device and are used for adjusting the flow of biogas entering the gas-liquid mixing device, and at least one valve and one flow meter are arranged between the doctor solution storage tank and the gas-liquid mixing device and are used for adjusting the flow of doctor solution.
12. The biogas desulfurization method according to claim 1, further comprising:
the circulating pump is respectively connected with the gas-liquid separation tank and the regeneration device and is used for pumping the sulfur-containing desulfurization solution in the gas-liquid separation tank into the regeneration device;
and the regulating valve is arranged between the circulating pump and the gas-liquid separation tank and is used for regulating the flow of the sulfur-containing desulfurization liquid in the gas-liquid separation tank into the regeneration device.
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| CN106118776A (en) * | 2016-08-03 | 2016-11-16 | 重庆康达新能源有限公司 | A kind of rubbish landfill gas desulfurizing and purifying system and desulfurizing and purifying method |
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| CN102133547B (en) * | 2011-03-02 | 2013-03-20 | 华南理工大学 | Ozone treatment regeneration method and device for vanadium titanium-based flue gas denitration catalyst |
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| CN106118776A (en) * | 2016-08-03 | 2016-11-16 | 重庆康达新能源有限公司 | A kind of rubbish landfill gas desulfurizing and purifying system and desulfurizing and purifying method |
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