CN109929636A - Biogas desulfurization method and device - Google Patents
Biogas desulfurization method and device Download PDFInfo
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- CN109929636A CN109929636A CN201711377764.2A CN201711377764A CN109929636A CN 109929636 A CN109929636 A CN 109929636A CN 201711377764 A CN201711377764 A CN 201711377764A CN 109929636 A CN109929636 A CN 109929636A
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Abstract
The present invention provides a kind of biogas desulfurization method and device, method includes the following steps: biogas is mixed with doctor solution make biogas microvesicle after carry out desulphurization reaction；The mixed liquor of biogas and doctor solution after desulfurization process is subjected to gas-liquid separation and obtains desulfurization biogas and sulfur-bearing doctor solution；Purified treatment is dried in desulfurization biogas；Sulfur-bearing doctor solution is subjected to desulfurization regeneration processing under metal phthalocyanine catalyst and oxygen effect, the sulfur-bearing doctor solution after regeneration treatment recycles after separating treatment as doctor solution.The device includes: the Liqiud-gas mixing device equipped with inlet port and outlet port, the reactor that import is connected with Liqiud-gas mixing device discharge port, the gas-liquid separation pond being connected with reactor, the dry decontamination device being connected with gas-liquid separation pond, the regenerating unit being connected respectively with Liqiud-gas mixing device and gas-liquid separate tank.This method and device are capable of increasing contact area, improve desulfuration efficiency, reduce catalyst loss.
Description
Technical field
The present invention relates to environmental technology field, in particular to a kind of biogas desulfurization method and device.
Background technique
Biogas is gradually paid attention to by society as renewable and clean energy resource in the case where pollution problem is increasingly prominent.Due to
Hydrogen sulfide gas is usually contained in biogas, the harmful substances such as sulfur dioxide easily generated after burning, therefore, biogas is before the use
It must carry out desulfurization process.
Currently, the domestic technique for being used for biogas desulfurization, it is de- can be specifically divided into bioanalysis desulfurization, dry desulfurization and wet process
Three kinds of sulphur.Wherein, biological desulphurization is to release the sulphur contained by it using microorganism or the enzymatic sulfur-containing compound contained by it
The process come, can substantially be divided into She11-Paques technique, Bio-SR technique and biochemical iron-alkali solution catalyzing.Biological desulphurization
With catalyst and oxidant is not required to, it is not required to processing chemical sludge, generates seldom biological pollution, sulphur, efficiency are recycled in low energy consumption
The advantages that height, odorless.But since biological desulphurization reaction speed is slower, and process is not easy to control, and condition requires harsh, frequent fortune
Occur the desulfuration efficiency decline of unknown cause during row, therefore, hinders the heavy industrialization application of biological desulphurization.
Dry desulfurization can be divided into chemiadsorption, chemical absorption method and catalytic oxidation, mainly by iron oxide process and
Oxidation of Hydrogen Sulfide is become sulfur-containing oxide by the solid desulfurating agents such as active carbon, to achieve the purpose that remove hydrogen sulfide.Dry method is de-
Sulphur is generally used for the lower biogas of sulfide hydrogen ingredient, if hydrogen sulfide gas content is higher, desulfurizing agent is quickly invalidated, to make to take off
Sulphur efficiency sharply declines, in addition, regenerating active carbon needs 400 DEG C or more of superheated steam, and when desulfurizing tower tower diameter is larger or material
When layer is higher, regeneration is incomplete.Iron oxide regeneration needs oxygen, if misoperation may explode in biogas environment, danger
Dangerous height, and iron oxide reproduction speed is slower.
Wet oxidation desulfurization method is chemical reaction desulfurization, including ammonium hydroxide liquid catalytic, mimosa extract method, KCA method, complexing
Iron processes etc., wherein of greatest concern with complex iron, it not only has excellent catalysis oxidation ability, but also cheap, overall next
It sees, some waste water handling problems exist in the prior art in wet desulphurization, and it is low that there are desulfuration efficiencies, and catalyst is easy to run off, utilization rate
It is not high.
Summary of the invention
In view of this, the present invention provides a kind of biogas desulfurization method.
The present invention also provides a kind of methane-desulfurizing devices.
In order to solve the above technical problems, the invention adopts the following technical scheme:
Biogas desulfurization method according to an embodiment of the present invention, comprising the following steps:
S1, biogas is sufficiently mixed with doctor solution make the biogas microvesicle after carry out desulfurization process and react；
S2, the mixed liquor of biogas and doctor solution after desulfurization process carries out to gas-liquid separation obtains desulfurization biogas and sulfur-bearing takes off
Sulphur liquid；
S3, purified treatment is dried in the obtained desulfurization biogas；
S4, the obtained sulfur-bearing doctor solution is carried out at desulfurization regeneration under the action of metal phthalocyanine catalyst and oxygen
Reason, the sulfur-bearing doctor solution after regeneration treatment remake doctor solution after separating treatment and recycle.
It further, in the step S1, include the mixed of sodium carbonate or sodium carbonate and sodium bicarbonate in the doctor solution
Close object.
Further, the step S4 the following steps are included:
S41, the sulfur-bearing doctor solution is added in the regenerating unit equipped with metal phthalocyanine catalyst, Xiang Suoshu regenerating unit
In be passed through oxygen carry out desulfurization regeneration processing, generate elemental sulfur；
S42, it the elemental sulfur of generation is isolated from the sulfur-bearing doctor solution after the regeneration treatment respectively obtains list
Liquid after matter sulphur and desulfurization process, liquid is recycled as doctor solution after the desulfurization process.
Further, in the step S4, the metal phthalocyanine catalyst is the phthalocyanine loaded on titanium foam
Co catalysts.
Further, the phthalocyanine cobalt catalyst is loaded into the method on titanium foam the following steps are included:
Glacial acetic acid and ethanol solution are prepared, Cobalt Phthalocyanine and dinethylformamide is added into solution respectively and is stirred molten
Solution, is slow added into sodium hydroxide solution, until raw material is completely dissolved, then titanium foam is added into mixed solution；
Solution equipped with titanium foam is placed in hydrothermal reaction kettle by ultrasonic treatment and is reacted at a temperature of 250 DEG C
4h obtains that treated titanium foam；
It takes out treated the titanium foam and is dried and is sintered, obtain the phthalein loaded on titanium foam
Cyanines Co catalysts.
Further, the phthalocyanine cobalt catalyst is being loaded in the method on titanium foam, the glacial acetic acid, second
Alcohol, Cobalt Phthalocyanine, dinethylformamide and titanium foam mass ratio be 5:30:1:2.5:4.
Further, to it is described treated titanium foam is sintered when, first will treated the titanium
Foam 260 DEG C at a temperature of be sintered 1h, then 350 DEG C at a temperature of be sintered 2h.
Biogas desulfurization method according to an embodiment of the present invention by the above process effectively mentions biogas microvesicle with step
High desulfurization efficiency, the phthalocyanine cobalt catalyst loaded on titanium foam can reduce catalyst loss, improve catalyst and utilize
Rate, while foam type load body surface area is larger, increases reaction contact area, is conducive to desulfurization regeneration.
Methane-desulfurizing device according to an embodiment of the present invention, comprising:
Liqiud-gas mixing device, the Liqiud-gas mixing device are respectively provided with feed inlet and the row that biogas and doctor solution is added
The discharge port of the mixed liquor of biogas and doctor solution out, the Liqiud-gas mixing device be used for mix be added the biogas and it is described take off
Sulphur liquid and by the biogas microvesicle；
Reactor, the import of the reactor are connected with by the gas with the discharge port of the Liqiud-gas mixing device
The mixed liquor in liquid mixing arrangement is added in the reactor and carries out desulphurization reaction；
Gas-liquid separation pond, the gas-liquid separation pond are connected with mixed after reacting in the reactor with the reactor
Liquid is closed to be transferred to progress gas-liquid separation in the gas-liquid separation pond and obtain desulfurization biogas and sulfur-bearing doctor solution；
Dry decontamination device, the dry decontamination device are connected for containing simultaneously dry decontamination with the gas-liquid separation pond
The desulfurization biogas isolated in the gas-liquid separation pond；
Regenerating unit, the regenerating unit are connected with the Liqiud-gas mixing device and the gas-liquid separation pond respectively, use
The sulfur-bearing doctor solution isolated in the gas-liquid separation pond regenerates, and the elemental sulfur generated in regeneration is isolated
After obtain after desulfurization process liquid and be transferred in the Liqiud-gas mixing device to mix as doctor solution with the biogas.
Further, the Liqiud-gas mixing device is gas-liquid mixing pump, and the reactor is baffled reactor.
Further, the titanium foam of supported metal phthalocyanine catalyst is equipped in the regenerating unit.
Further, the bottom of the regenerating unit is taper and is equipped in the bottom for the list generated to be discharged
The sulphur outlet of matter sulphur controls the switch of the sulphur outlet in the sulphur outlet equipped with controlled valve by the controlled valve.
Further, the methane-desulfurizing device further include:
Bubbler, the bubbler are arranged in the regenerating unit for being passed through air or oxygen to the sulfur-bearing doctor solution
Gas.
Further, the methane-desulfurizing device further include:
Biogas storage tank, the biogas storage tank is connected with the Liqiud-gas mixing device, for storing the biogas simultaneously
The Liqiud-gas mixing device is added in the biogas；
Doctor solution storage pool, the doctor solution storage pool are connected with the Liqiud-gas mixing device and the regenerating unit respectively
It is logical, for store regenerated in the regenerating unit after liquid and liquid after the desulfurization process is added after the obtained desulfurization process
The Liqiud-gas mixing device is mixed as doctor solution with the biogas.
Further, the methane-desulfurizing device further include:
At least two valves and two flowmeters, at least one described valve and a flowmeter are located at the biogas
For adjusting the flow into the biogas of the Liqiud-gas mixing device between holding vessel and the Liqiud-gas mixing device, at least
One valve and a flowmeter are located between the doctor solution storage pool and the Liqiud-gas mixing device for adjusting
Save the flow of the doctor solution.
Further, the methane-desulfurizing device further include:
Circulating pump, the circulating pump are connected with the gas-liquid separation pond and the regenerating unit respectively, are used for the gas
The sulfur-bearing doctor solution in liquid separate tank is pumped into the regenerating unit；
Control valve, the control valve are located between the circulating pump and the gas-liquid separation pond for adjusting the gas
The sulfur-bearing doctor solution in liquid separate tank enters the flow of the regenerating unit.
The advantageous effects of the above technical solutions of the present invention are as follows:
Biogas microvesicle can be improved desulfuration efficiency, load to titanium by methane-desulfurizing device according to an embodiment of the present invention
Phthalocyanine cobalt catalyst on metal foam can reduce catalyst loss, improve catalyst utilization, increase reaction contact area,
Be conducive to desulfurization regeneration, improve regeneration efficiency, and the apparatus structure is simple, it is easy to accomplish.
Detailed description of the invention
Fig. 1 is the flow diagram of the biogas desulfurization method of one embodiment of the invention；
Fig. 2 is the connection schematic diagram of the methane-desulfurizing device of one embodiment of the invention.
Appended drawing reference:
Methane-desulfurizing device 100；
Liqiud-gas mixing device 10；
Reactor 20；
Gas-liquid separation pond 30；
Dry decontamination device 40；
Regenerating unit 50；Titanium foam 51；Bubbler 52；Controlled valve 53；
Biogas storage tank 60；Valve 61；Flowmeter 62；
Doctor solution storage pool 70；
Circulating pump 80；Control valve 81.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
Attached drawing, the technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, ordinary skill
Personnel's every other embodiment obtained, shall fall within the protection scope of the present invention.
Biogas desulfurization method according to an embodiment of the present invention is specifically described with reference to the accompanying drawing.
As shown in Figure 1, biogas desulfurization method according to an embodiment of the present invention, comprising the following steps:
Biogas is sufficiently mixed with doctor solution after making biogas microvesicle and carries out desulfurization process and react by step S1.
In this step, the component content first in analysis detection biogas, sulphur-containing substance such as hydrogen sulfide, sulfurous organic compound
Type and content measure the physical characteristics such as the temperature of biogas, and desulfurizing agent may include sodium carbonate in doctor solution, can be according to biogas
Proper amount of sodium carbonate is added into doctor solution for the content of middle hydrogen sulfide gas, prepares certain density sodium carbonate liquor, de-
Sulphur liquid carries out the concentration that can measure sodium carbonate in doctor solution during desulfurization at regular intervals, if concentration of sodium carbonate is inclined
It is low, it can continue to react after sodium carbonate is added.
Also it may include the mixture of sodium carbonate and sodium bicarbonate in doctor solution, the content of sodium carbonate and sodium bicarbonate can be with
It reasonably selects, also can according to need and ammonium hydroxide, quick lime etc. is added, taken off according in the adjustable doctor solution of the content of sulphur in biogas
The content of sulphur agent ammonium hydroxide, quick lime, sodium carbonate and sodium bicarbonate adjusts temperature, the pH value of doctor solution, and the temperature of doctor solution can
To be selected between 30 DEG C -70 DEG C, it is conducive to desulphurization reaction and carries out, so that desulphurization reaction process is easy to carry out, according to sulphur in biogas
The mixed proportion of the type and proportion adjustment biogas and desulfurizing agent of content and desulfurizing agent, so that biogas and doctor solution are sufficiently mixed
It closes, makes biogas microvesicle.When in doctor solution including sodium carbonate and sodium bicarbonate, the key reaction of entire sweetening process is as follows:
De- H2The chemical absorbing reaction such as following reaction equations (1) of S:
H2S+Na2CO3→NaHS+NaHCO3 (1)
The chemical absorbing reaction such as following reaction equations (2) of removal of organic sulfur:
COS+2Na2CO3+H2O→Na2CO2S+2NaHCO3 (2)
Biogas microvesicle can be realized by stirring, biogas microvesicle can also be made by gas-liquid mixing pump, increase anti-
Contact area is answered, is conducive to reaction and carries out, the content of sulphur in biogas is detected after the desulphurization reaction of certain time, after meeting the requirements
Complete desulphurization reaction, increase the gas liquid interfacial area of desulphurization reaction system by making biogas microvesicle, improve desulfuration efficiency and
Desulfurization effect.
The mixed liquor progress gas-liquid separation of biogas and doctor solution after desulfurization process is obtained desulfurization biogas and contained by step S2
Sulphur doctor solution.
In this step, stop desulphurization reaction after doctor solution desulfurization process reaction biogas reaches requirement in step S1,
Mixture after microvesicle biogas and doctor solution reaction is subjected to gas-liquid separation, obtains desulfurization biogas and sulfur-bearing doctor solution, it can be with
Mixture after microvesicle biogas and doctor solution reaction is transferred to separator, it, can be to mixed liquor during gas-liquid separation
Vacuum is extracted, the pressure of mixed liquor container containing is reduced, while stirring can also be increased, accelerates desulfurization biogas from sulfur-bearing doctor solution
In isolate, desulfurization biogas obtained after separation and sulfur-bearing doctor solution can be transferred to respectively in corresponding reservoir, in case after
The continuous dry decontamination to desulfurization biogas is handled, and the regeneration treatment to sulfur-bearing doctor solution.
Purified treatment is dried in obtained desulfurization biogas by step S3.
In this step, purified treatment is dried in obtained desulfurization biogas, desulfurization biogas can be transferred to dry dress
It is dried in setting, removes the water etc. in desulfurization biogas, the desulfurization biogas after drying can be transferred to purification absorption dress
In setting, remaining a small amount of impurity in desulfurization biogas is further removed by adsorbent, improves the cleannes of biogas.
Step S4 carries out obtained sulfur-bearing doctor solution at desulfurization regeneration under the action of metal phthalocyanine catalyst and oxygen
Reason, the sulfur-bearing doctor solution after regeneration treatment remake doctor solution after separating treatment and recycle.
In this step, sulfur-bearing doctor solution obtained after separation can be placed in reactor, gold is added in the reactor
Belong to phthalocyanine catalyst, metal phthalocyanine catalyst can be the metal phthalocyanines such as metal phthalocyanine zinc, metal phthalocyanine iron, metal phthalocyanine nickel
Object is closed, metal phthalocyanine catalyst can be the phthalocyanine cobalt catalyst loaded on titanium foam, and metal phthalocyanine catalyst can be with
It is supported on carrier foam, increases the reaction contact area of catalyst and sulfur-bearing doctor solution, while being passed through into sulfur-bearing doctor solution
Oxygen or air carry out desulfurization regeneration processing under the action of metal phthalocyanine catalyst and oxygen, make in metal phthalocyanine catalyst
Under, oxygen is reacted with sulfur-bearing doctor solution generates sulphur simple substance, and reaction staticly settles after a certain period of time, and sulphur is deposited to reactor bottom
Portion can isolate sulphur simple substance from the opening of reactor bottom, and the doctor solution after regenerating can flow back into doctor solution storage
It deposits tank to continue to use with biogas mixing circulation, reduces the usage amount of doctor solution, improve the utilization rate of doctor solution.
In above-mentioned steps of the invention and in the process, by biogas microvesicle, increases reaction contact area, effectively improve desulfurization
Efficiency, sulfur-bearing doctor solution carry out desulfurization regeneration processing under the action of metal phthalocyanine catalyst and oxygen, can effectively remove and contain
Sulphur in sulphur doctor solution, is conducive to desulfurization regeneration.
It according to one embodiment of present invention, in step sl, may include sodium carbonate or sodium carbonate and carbon in doctor solution
The content of the mixture of sour hydrogen sodium, sodium carbonate can reasonably select according to the actual situation, and the mass fraction of sodium carbonate can be
It can also simultaneously include sodium carbonate and sodium bicarbonate in doctor solution between 3%-15%, the mass fraction of sodium bicarbonate can be
Between 2%-9%, the ratio and content of sodium carbonate and sodium bicarbonate also can according to need reasonable selection.
In some embodiments of the invention, step S4 may comprise steps of:
Sulfur-bearing doctor solution is added in the regenerating unit equipped with metal phthalocyanine catalyst, leads into regenerating unit by step S41
Enter oxygen and carry out desulfurization regeneration processing, generates elemental sulfur；
The elemental sulfur of generation is isolated from the sulfur-bearing doctor solution after regeneration treatment and respectively obtains elemental sulfur by step S42
With liquid after desulfurization process, liquid is recycled as doctor solution after desulfurization process.
That is, sulfur-bearing doctor solution can be added to the regenerating unit that metal phthalocyanine catalyst is housed in step S41
In, metal phthalocyanine catalyst is placed in sulfur-bearing doctor solution, while being passed through air or oxygen into sulfur-bearing doctor solution, in metal phthalocyanine
Desulfurization regeneration processing is carried out under the action of catalyst and oxygen, the temperature of sulfur-bearing doctor solution may be selected between 30 DEG C -80 DEG C, have
Conducive to regenerative response progress, under metal phthalocyanine catalyst effect, oxygen reacts generation with the sulphur-containing substance in sulfur-bearing doctor solution
Sulphur simple substance, when in doctor solution including sodium carbonate and sodium bicarbonate, the key reaction in reaction process is as follows:
Catalysis oxidation analyses reaction of Salmon-Saxl such as following formula (3) to formula (6):
NaHS+(X-1)S+NaHCO3→Na2SX+CO2+H2O (3)
Sulphur simple substance is converted by sulphur-containing substance consequently facilitating separating, and realizes that sulfur-bearing desulfurization regeneration, metal phthalocyanine are urged
Agent can be supported on titanium foam, catalyst is supported on titanium foam, catalyst is enabled to be fixed,
The loss for reducing catalyst, improves the utilization rate of catalyst, is capable of increasing the contact area of catalyst Yu sulfur-bearing doctor solution, improves
Reaction efficiency.
In step S42, the elemental sulfur of generation is isolated from the sulfur-bearing doctor solution after regeneration treatment and respectively obtains list
Liquid after matter sulphur and desulfurization process, sulphur simple substance is sunk after precipitating gets together, the elemental sulfur that then heavy can will get together and
Liquid separates after desulfurization process, and liquid can be used as doctor solution and recycle after desulfurization process, liquid after desulfurization process can be stored
In holding vessel.
Other specific embodiments according to the present invention, in step s 4, metal phthalocyanine catalyst can be to load to titanium
Phthalocyanine cobalt catalyst on metal foam loads to phthalocyanine cobalt catalyst on titanium foam, can increase Cobalt Phthalocyanine catalysis
The contact area of agent and sulfur-bearing doctor solution promotes the progress of regenerative response, improves regeneration rate, and phthalocyanine cobalt catalyst is fixed on titanium
The loss that catalyst can be reduced on metal foam, improves the utilization rate of catalyst.
It according to some embodiments of the present invention, include following by the method that phthalocyanine cobalt catalyst loads on titanium foam
Step:
It takes proper amount of glacial acetic acid and ethyl alcohol to prepare solution, Cobalt Phthalocyanine is added into the glacial acetic acid and ethanol solution of preparation,
Dinethylformamide and continuous stirring and dissolving are added, is slow added into sodium hydroxide solution, hydrogen-oxygen after stirring a period of time
Change the pH of sodium solution between 8.5-9.0, until raw material is completely dissolved in solution, finally addition titanium steeps into solution again
Foam；
Solution equipped with titanium foam is placed in hydrothermal reaction kettle by ultrasonic treatment and is reacted at a temperature of 250 DEG C
4h obtains that treated titanium foam, specific reaction temperature and time can also reasonably adjust according to the actual situation, reaction temperature
Degree can be gradually warmed up, and heating rate can reasonably select, and be can choose as the heating rate of 5 DEG C/min, after reaction may be used
It is cooling with Temperature fall；
It takes out treated titanium foam and is dried and is sintered, sintering temperature and time can be according to the actual situation
It reasonably selects, heating rate when sintering can obtain the Cobalt Phthalocyanine loaded on titanium foam according to practical reasonable selection
Catalyst.
In some embodiments of the invention, phthalocyanine cobalt catalyst is being loaded in the method on titanium foam, ice
Acetic acid, ethyl alcohol, Cobalt Phthalocyanine, dinethylformamide and titanium foam mass ratio can be 5:30:1:2.5:4, specifically
Mass ratio can also be adjusted rationally according to the actual situation, and the Cobalt Phthalocyanine loaded on titanium foam obtained under this ratio is urged
Agent is preferable.
Some specific embodiments according to the present invention, to treated titanium foam is sintered when, can first by
Treated titanium foam 260 DEG C at a temperature of be sintered 1h, can be heated up with suitable heating rate, for example, with 5 DEG C/
Min heating rate from room temperature to 260 DEG C, then 350 DEG C at a temperature of be sintered 2h, can also be with the heating of 5 DEG C/min speed
Rate is warming up to 350 DEG C, and the phthalocyanine cobalt catalyst loaded on titanium foam can be obtained in cooling after sintering, so that phthalocyanine
Co catalysts are fixed on titanium foam, reduce catalyst loss, increase contact area.
Biogas desulfurization method according to an embodiment of the present invention by biogas microvesicle, increases gas by the above process and step
Liquid contact area, effectively improves desulfuration efficiency, and phthalocyanine cobalt catalyst, which is supported on titanium foam, can reduce catalyst stream
It loses, improves catalyst utilization, while foam type load body surface area is larger, increases reaction contact area, is conducive to doctor solution
Regeneration.
Further biogas desulfurization method is illustrated below with reference to some specific embodiments.
Embodiment 1
Biogas is sufficiently mixed with doctor solution after making biogas microvesicle and carries out desulfurization process and react, can first configure certain matter
The sodium carbonate doctor solution of score is measured, the mass fraction of sodium carbonate can be 6% in doctor solution, and doctor solution temperature can be 30 DEG C,
Concentration of sodium carbonate in doctor solution can be measured at regular intervals, for example, it can be spaced 15min, if concentration of sodium carbonate is relatively low,
Reaction can be fixed tentatively, reacts and continues after addition sodium carbonate；The mixed liquor of biogas and doctor solution after desulfurization process is carried out
Gas-liquid separation obtains desulfurization biogas and sulfur-bearing doctor solution；Obtained desulfurization biogas is dried at purification by drying device
Reason；It is added in obtained sulfur-bearing doctor solution and loads to phthalocyanine cobalt catalyst on titanium foam, while to sulfur-bearing doctor solution
In be passed through oxygen, sulfur-bearing doctor solution temperature can be 40 DEG C, and desulfurization regeneration processing is carried out under the action of catalyst and oxygen, raw
At elemental sulfur, the elemental sulfur of generation is isolated from the sulfur-bearing doctor solution after regeneration treatment and respectively obtains elemental sulfur and desulfurization place
Liquid after reason, liquid is recycled as doctor solution after desulfurization process.The Cobalt Phthalocyanine loaded on titanium foam in the present embodiment is urged
Agent the preparation method is as follows:
It takes 5 parts of (mass parts) glacial acetic acid and 30 parts of ethyl alcohol to prepare mixed solution, weighs 1 part of Cobalt Phthalocyanine and mixed solution is added
In, 2.5 parts of dinethylformamides are added, 20min is continuously stirred, being slow added into sodium hydroxide solution, (pH is in 8.5-
9.0), until raw material is completely dissolved, 4 parts of titanium foams is eventually adding and are soaked in mixed solution, be ultrasonically treated 20min, turned
Enter in hydrothermal reaction kettle, is warming up to 250 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 4h, then natural cooling.Treated for taking-up
Titanium foam is simultaneously dried and is sintered, and with the heating rate of 5 DEG C/min from room temperature to 260 DEG C, is sintered 1h, then with 5
DEG C/heating rate of min is warming up to 350 DEG C, after re-sintering 2h, after natural cooling, obtains and load on titanium foam
Phthalocyanine cobalt catalyst.
Biogas desulfurization method according to an embodiment of the present invention by biogas microvesicle, increases gas by the above process and step
Liquid contact area, effectively improves desulfuration efficiency, can be subtracted using the phthalocyanine cobalt catalyst of preparation loaded on titanium foam
Few catalyst loss improves catalyst utilization, while foam type load body surface area is larger, increases reaction contact area, has
Conducive to desulfurization regeneration.
Embodiment 2
Biogas is sufficiently mixed with doctor solution after making biogas microvesicle and carries out desulfurization process and react, can first configure certain matter
The sodium carbonate doctor solution of score is measured, the mass fraction of sodium carbonate can be 6% in doctor solution, and doctor solution temperature can be 45 DEG C,
Concentration of sodium carbonate in doctor solution can be measured at regular intervals, for example, it can be spaced 20min, if concentration of sodium carbonate is relatively low,
Reaction can be fixed tentatively, reacts and continues after addition sodium carbonate；The mixed liquor of biogas and doctor solution after desulfurization process is carried out
Gas-liquid separation obtains desulfurization biogas and sulfur-bearing doctor solution；Obtained desulfurization biogas is dried at purification by drying device
Reason；It is added in obtained sulfur-bearing doctor solution and loads to phthalocyanine cobalt catalyst on titanium foam, while to sulfur-bearing doctor solution
In be passed through oxygen, sulfur-bearing doctor solution temperature is 50 DEG C, and desulfurization regeneration processing is carried out under the action of catalyst and oxygen, is generated single
Matter sulphur, by the elemental sulfur of generation after being isolated in the sulfur-bearing doctor solution after regeneration treatment and respectively obtaining elemental sulfur and desulfurization process
Liquid, liquid is recycled as doctor solution after desulfurization process.The phthalocyanine cobalt catalyst on titanium foam is loaded in the present embodiment
The preparation method is as follows:
It takes 5 parts of (mass parts) glacial acetic acid and 30 parts of ethyl alcohol to prepare mixed solution, weighs 1 part of Cobalt Phthalocyanine and mixed solution is added
In, 2.5 parts of dinethylformamides are added, 20min is continuously stirred, being slow added into sodium hydroxide solution, (pH is in 8.5-
9.0), until raw material is completely dissolved, 4 parts of titanium foams is eventually adding and are soaked in mixed solution, be ultrasonically treated 20min, turned
Enter in hydrothermal reaction kettle, is warming up to 250 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 4h, then natural cooling.Treated for taking-up
Titanium foam is simultaneously dried and is sintered, and with the heating rate of 5 DEG C/min from room temperature to 260 DEG C, is sintered 1h, then with 5
DEG C/heating rate of min is warming up to 350 DEG C, after re-sintering 2h, after natural cooling, obtains and load on titanium foam
Phthalocyanine cobalt catalyst.
Biogas desulfurization method according to an embodiment of the present invention by biogas microvesicle, increases gas by the above process and step
Liquid contact area, effectively improves desulfuration efficiency, can be subtracted using the phthalocyanine cobalt catalyst of preparation loaded on titanium foam
Few catalyst loss, increases reaction contact area, is conducive to desulfurization regeneration.
Embodiment 3
Biogas is sufficiently mixed with doctor solution after making biogas microvesicle and carries out desulfurization process and react, can first configure certain matter
The sodium carbonate of score and the doctor solution of sodium bicarbonate are measured, the mass fraction of sodium carbonate can be 6% in doctor solution, sodium bicarbonate
Mass fraction can be 3%, and doctor solution temperature can be 60 DEG C, can be spaced sodium carbonate and carbonic acid in 15min measurement doctor solution
Hydrogen na concn can fix tentatively reaction if the concentration of sodium carbonate or sodium bicarbonate is relatively low, be added after sodium carbonate or sodium bicarbonate instead
It should continue；The mixed liquor progress gas-liquid separation of biogas and doctor solution after desulfurization process is obtained into desulfurization biogas and sulfur-bearing takes off
Sulphur liquid；Purified treatment is dried by drying device in obtained desulfurization biogas；It is added in obtained sulfur-bearing doctor solution negative
The phthalocyanine cobalt catalyst being downloaded on titanium foam, while oxygen is passed through into sulfur-bearing doctor solution, sulfur-bearing doctor solution temperature is 55
DEG C, desulfurization regeneration processing is carried out under the action of catalyst and oxygen, generates elemental sulfur, by the elemental sulfur of generation from regeneration treatment
Liquid after respectively obtaining elemental sulfur and desulfurization process is isolated in sulfur-bearing doctor solution afterwards, liquid is recycled as doctor solution after desulfurization process
It utilizes.Loaded in the present embodiment the phthalocyanine cobalt catalyst on titanium foam the preparation method is as follows:
It takes 5 parts of (mass parts) glacial acetic acid and 30 parts of ethyl alcohol to prepare mixed solution, weighs 1 part of Cobalt Phthalocyanine and mixed solution is added
In, 2.5 parts of dinethylformamides are added, 20min is continuously stirred, being slow added into sodium hydroxide solution, (pH is in 8.5-
9.0), until raw material is completely dissolved, 4 parts of titanium foams is eventually adding and are soaked in mixed solution, be ultrasonically treated 20min, turned
Enter in hydrothermal reaction kettle, is warming up to 250 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 4h, then natural cooling.Treated for taking-up
Titanium foam is simultaneously dried and is sintered, and with the heating rate of 5 DEG C/min from room temperature to 260 DEG C, is sintered 1h, then with 5
DEG C/heating rate of min is warming up to 350 DEG C, after re-sintering 2h, after natural cooling, obtains and load on titanium foam
Phthalocyanine cobalt catalyst.
Biogas desulfurization method according to an embodiment of the present invention by biogas microvesicle, increases gas by the above process and step
Liquid contact area is improved desulfuration efficiency, can be reduced and be urged using the phthalocyanine cobalt catalyst of preparation loaded on titanium foam
Agent is lost, and increases reaction contact area, accelerates desulfurization regeneration rate.
Embodiment 4
Biogas is sufficiently mixed with doctor solution after making biogas microvesicle and carries out desulfurization process and react, first configures certain mass point
The doctor solution of several sodium carbonate and sodium bicarbonate, the mass fraction of sodium carbonate can be 9% in doctor solution, the quality of sodium bicarbonate
Score can be 3%, and doctor solution temperature can be 70 DEG C, can measure sodium carbonate and bicarbonate in doctor solution at interval of 15min
Na concn can fix tentatively reaction if the concentration of sodium carbonate or sodium bicarbonate is relatively low, react after sodium carbonate or sodium bicarbonate is added
Continue；The mixed liquor of biogas and doctor solution after desulfurization process is subjected to gas-liquid separation and obtains desulfurization biogas and sulfur-bearing desulfurization
Liquid；Purified treatment is dried by drying device in obtained desulfurization biogas；Load is added in obtained sulfur-bearing doctor solution
Phthalocyanine cobalt catalyst onto titanium foam, while oxygen is passed through into sulfur-bearing doctor solution, sulfur-bearing doctor solution temperature is 72 DEG C,
Desulfurization regeneration processing is carried out under the action of catalyst and oxygen, elemental sulfur is generated, by the elemental sulfur of generation after regeneration treatment
Sulfur-bearing doctor solution in isolate respectively obtain elemental sulfur and desulfurization process after liquid, liquid recycles benefit as doctor solution after desulfurization process
With.Loaded in the present embodiment the phthalocyanine cobalt catalyst on titanium foam the preparation method is as follows:
It takes 5 parts of (mass parts) glacial acetic acid and 30 parts of ethyl alcohol to prepare mixed solution, weighs 1 part of Cobalt Phthalocyanine and mixed solution is added
In, 2.5 parts of dinethylformamides are added, 20min is continuously stirred, being slow added into sodium hydroxide solution, (pH is in 8.5-
9.0), until raw material is completely dissolved, 4 parts of titanium foams is eventually adding and are soaked in mixed solution, be ultrasonically treated 20min, turned
Enter in hydrothermal reaction kettle, is warming up to 250 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 4h, then natural cooling.Treated for taking-up
Titanium foam is simultaneously dried and is sintered, and with the heating rate of 5 DEG C/min from room temperature to 260 DEG C, is sintered 1h, then with 5
DEG C/heating rate of min is warming up to 350 DEG C, after re-sintering 2h, after natural cooling, obtains and load on titanium foam
Phthalocyanine cobalt catalyst.
Biogas desulfurization method according to an embodiment of the present invention by biogas microvesicle, increases gas by the above process and step
Liquid contact area is improved desulfuration efficiency, can be reduced and be urged using the phthalocyanine cobalt catalyst of preparation loaded on titanium foam
Agent is lost, and increases reaction contact area, accelerates desulfurization regeneration rate.
Embodiment 5
Biogas is sufficiently mixed with doctor solution after making biogas microvesicle and carries out desulfurization process and react, first configuration contains sodium carbonate
With the doctor solution of sodium bicarbonate, the mass fraction of sodium carbonate can be 7% in doctor solution, and the mass fraction of sodium bicarbonate is can be with
2%, doctor solution temperature can be 70 DEG C, at interval of sodium carbonate and sodium bicarbonate concentration in 30min measurement doctor solution, if sodium carbonate
Or the concentration of sodium bicarbonate is relatively low, then can fix tentatively reaction, react and continue after addition sodium carbonate or sodium bicarbonate；By desulfurization
The mixed liquor of treated biogas and doctor solution carries out gas-liquid separation and obtains desulfurization biogas and sulfur-bearing doctor solution；The desulfurization that will be obtained
Purified treatment is dried by drying device in biogas；It is added and is loaded on titanium foam in obtained sulfur-bearing doctor solution
Phthalocyanine cobalt catalyst, while oxygen is passed through into sulfur-bearing doctor solution, sulfur-bearing doctor solution temperature are 67 DEG C, in catalyst and oxygen
Effect is lower to carry out desulfurization regeneration processing, generates elemental sulfur, and the elemental sulfur of generation is divided from the sulfur-bearing doctor solution after regeneration treatment
Liquid after respectively obtaining elemental sulfur and desulfurization process is separated out, liquid is recycled as doctor solution after desulfurization process.It is born in the present embodiment
Be downloaded to the phthalocyanine cobalt catalyst on titanium foam the preparation method is as follows:
It takes 5 parts of (mass parts) glacial acetic acid and 30 parts of ethyl alcohol to prepare mixed solution, weighs 1 part of Cobalt Phthalocyanine and mixed solution is added
In, 2.5 parts of dinethylformamides are added, 20min is continuously stirred, being slow added into sodium hydroxide solution, (pH is in 8.5-
9.0), until raw material is completely dissolved, 4 parts of titanium foams is eventually adding and are soaked in mixed solution, be ultrasonically treated 20min, turned
Enter in hydrothermal reaction kettle, is warming up to 250 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 4h, then natural cooling.Treated for taking-up
Titanium foam is simultaneously dried and is sintered, and with the heating rate of 5 DEG C/min from room temperature to 260 DEG C, is sintered 1h, then with 5
DEG C/heating rate of min is warming up to 350 DEG C, after re-sintering 2h, after natural cooling, obtains and load on titanium foam
Phthalocyanine cobalt catalyst.
Biogas desulfurization method according to an embodiment of the present invention by biogas microvesicle, increases gas by the above process and step
Liquid contact area is improved desulfuration efficiency, can be reduced and be urged using the phthalocyanine cobalt catalyst of preparation loaded on titanium foam
Agent is lost, and increases reaction contact area, accelerates desulfurization regeneration rate.
Above-mentioned some embodiments are only the embodiments of optimization, and protection scope of the present invention is not limited only to above-described embodiment
Method and process, biogas desulfurization method according to an embodiment of the present invention by the above process increase biogas microvesicle with step
Big gas liquid interfacial area, effectively improves desulfuration efficiency, utilizes the phthalocyanine cobalt catalyst energy of preparation loaded on titanium foam
Catalyst loss is enough reduced, catalyst utilization is improved, while foam type load body surface area is larger, increases reaction contact surface
Product, is conducive to desulfurization regeneration.
The present invention also provides a kind of methane-desulfurizing devices 100.
As shown in Fig. 2, methane-desulfurizing device 100 includes Liqiud-gas mixing device 10, reactor 20, gas-liquid separation pond 30, does
Dry purification device 40 and regenerating unit 50.
Specifically, Liqiud-gas mixing device 10 is respectively provided with the feed inlet that biogas and doctor solution is added and discharge biogas
With the discharge port of the mixed liquor of doctor solution, Liqiud-gas mixing device 10 is used to mix the biogas and doctor solution and by biogas microvesicle of addition
Change；The import of reactor 20 is connected to add the mixed liquor in Liqiud-gas mixing device 10 with the discharge port of Liqiud-gas mixing device 10
Enter in reactor 20 and carries out desulphurization reaction；After gas-liquid separation pond 30 is connected with reactor 20 will react in reactor 20
Mixed liquor, which is transferred in gas-liquid separation pond 30, to carry out gas-liquid separation and obtains desulfurization biogas and sulfur-bearing doctor solution；Dry decontamination device 40
The desulfurization biogas being connected with gas-liquid separation pond 30 for containing and being isolated in dry decontamination gas-liquid separation pond 30；Regenerating unit
50 are connected with Liqiud-gas mixing device 10 and gas-liquid separate tank 30 respectively, for de- to the sulfur-bearing isolated in gas-liquid separation pond 30
Sulphur liquid is regenerated, and liquid after desulfurization process is obtained after the elemental sulfur generated in regeneration is isolated and is transferred to gas-liquid mixed dress
It sets in 10 and is mixed as doctor solution with biogas.
That is, methane-desulfurizing device 100 is mainly by Liqiud-gas mixing device 10, reactor 20, gas-liquid separation pond 30, dry
Dry purification device 40 and regenerating unit 50 are constituted, wherein can be respectively equipped with feed inlet and discharging on Liqiud-gas mixing device 10
Mouthful, specific location can be reasonably selected, be can be set in the bottom of Liqiud-gas mixing device 10, Liqiud-gas mixing device 10 can be gas
Liquid mixing pump can be the container with agitating device, and feed inlet can be used for being added biogas and doctor solution, and discharge port can be used
In the mixed liquor of discharge biogas and doctor solution, Liqiud-gas mixing device 10 can be used for mixing the biogas and doctor solution of addition, pass through
Biogas microvesicle, the biogas of microvesicle can be capable of increasing the contact area with doctor solution by Liqiud-gas mixing device 10, be promoted de-
The progress of reaction of Salmon-Saxl improves desulfuration efficiency.Liqiud-gas mixing device 10 can be connected with reactor 20, and the import of reactor 20 can be with
It is connected with the discharge port of Liqiud-gas mixing device 10, the biogas of microvesicle and the mixture of doctor solution can in Liqiud-gas mixing device 10
To be transferred in reactor 20, mixture carries out desulphurization reaction in reactor 20, when the sulphur-containing substance in biogas has been deviate from
It can stop desulfurization.
Gas-liquid separation pond 30 can be connected with reactor 20, and the mixture desulfurization of the biogas and doctor solution of microvesicle is completed
The mixture after reacting in reactor 20 can be transferred in gas-liquid separation pond 30 afterwards and carry out gas-liquid separation, and obtain desulfurization biogas
With sulfur-bearing doctor solution, then desulfurization biogas and sulfur-bearing doctor solution can be handled respectively, desulfurization biogas can be done
Dry purified treatment can carry out regeneration treatment to sulfur-bearing doctor solution.Dry decontamination device 40 can be connected with gas-liquid separation pond 30
Logical, desulfurization biogas obtained after separation can be transferred in dry decontamination device 40, and dry decontamination device 40 can be used for containing simultaneously
The type and size of the desulfurization biogas isolated in dry decontamination gas-liquid separation pond 30, dry decontamination device 40 can be according to desulfurization
The dry decontamination amount of biogas reasonably selects.
Regenerating unit 50 can be connected with Liqiud-gas mixing device 10 and gas-liquid separate tank 30 respectively, can in regenerating unit 50
To be equipped with the device that can be passed through air or oxygen, it can be equipped with catalyst such as metal phthalocyanine catalyst, catalyst can be born
It is loaded on foams, isolated sulfur-bearing doctor solution can be transferred in regenerating unit 50 in gas-liquid separation pond 30, regenerating unit 50
It can be used for carrying out regeneration treatment to the sulfur-bearing doctor solution isolated in gas-liquid separation pond 30, sulfur-bearing doctor solution carried out at regeneration
Elemental sulfur can be generated after reason, the elemental sulfur of generation can be isolated from regenerating unit 50, obtained de- in regenerating unit 50
Liquid after desulfurization process can be transferred in Liqiud-gas mixing device 10 by liquid after sulphuring treatment, and liquid can be used as doctor solution after desulfurization process
It is further mixed in Liqiud-gas mixing device 10 with biogas, realizes recycling for doctor solution, improve the utilization rate of doctor solution.
Biogas microvesicle can be increased biogas and taken off by methane-desulfurizing device 100 according to an embodiment of the present invention as a result,
The contact area of sulphur liquid improves desulfuration efficiency, and regenerating unit 50 can regenerate sulfur-bearing doctor solution, realizes following for doctor solution
Ring utilizes, and by the utilization rate of doctor solution, and the apparatus structure is simple, it is easy to accomplish.
In one embodiment of the invention, Liqiud-gas mixing device 10 can be gas-liquid mixing pump, and gas-liquid mixing pump passes through
Suction function sucks biogas and doctor solution simultaneously, and biogas is sufficiently mixed with doctor solution completion under impeller of pump high speed rotation, with this
Biogas microvesicle is realized simultaneously, increases the gas liquid interfacial area of biogas and doctor solution reaction system, is increased desulphurization reaction speed, is mentioned
High desulfurization efficiency.
In another embodiment of the present invention, reactor 20 can be baffled reactor, in baffled reactor
Baffle plate can biogas to microvesicle in reactor 20 and doctor solution carry out flow-disturbing, promote desulphurization reaction to carry out.
In some embodiments of the invention, the titanium of supported metal phthalocyanine catalyst can be equipped in regenerating unit 50
Metal foam 51, the bottom and middle part in regenerating unit 50 respectively can be set in titanium foam 51, in order to titanium foam
51 can be placed in sulfur-bearing doctor solution, and titanium foam 51 is capable of increasing catalyst and connects with sulfur-bearing doctor solution in regenerating unit 50
Contacting surface product, enables metal phthalocyanine catalyst to have preferable facilitation to regenerative response, metal phthalocyanine catalyst is fixed on
On titanium foam 51, the loss of catalyst can be reduced, improves the utilization rate of catalyst.
In other embodiments of the invention, the bottom of regenerating unit 50 can be taper, and can be equipped in bottom
It for the sulphur outlet of the elemental sulfur generated to be discharged, is discharged conducive to the separation of elemental sulfur, controlled valve 53 can be equipped in sulphur outlet,
The switch that sulphur outlet is controlled by controlled valve 53 is easy to implement the discharge separation of elemental sulfur.
According to some embodiments of the present invention, methane-desulfurizing device 100 can also include bubbler 52, and bubbler 52 can be with
It is arranged on the suitable position in regenerating unit 50, the bottom of bubbler 52 can be located at, in order to which bubbler 52 can be to contains
Sulphur doctor solution is passed through air or oxygen, and when bubbler 52 is passed through air or oxygen to sulfur-bearing doctor solution, air or oxygen can
Rise in sulfur-bearing doctor solution, is conducive to oxygen and participates in regenerative response.
Other embodiments according to the present invention, methane-desulfurizing device 100 can also include biogas storage tank 60 and desulfurization
Liquid storage pool 70, wherein biogas storage tank 60 can be connected with Liqiud-gas mixing device 10, and biogas storage tank 60 can be used for storing up
Biogas is deposited, biogas can be added in Liqiud-gas mixing device 10 when Liqiud-gas mixing device 10 is opened, it can also be in biogas storage
Installation buffering stable-pressure device between tank 60 and Liqiud-gas mixing device 10, for example, buffering pressure stabilizing dress can be pressure reducing valve, it can be slow
Tank is rushed, biogas is steadily entered in Liqiud-gas mixing device 10.
Doctor solution storage pool 70 can be connected with Liqiud-gas mixing device 10 and regenerating unit 50 respectively, for storing regeneration
Liquid after desulfurization process obtained after separation is regenerated in device 50, and conduct in Liqiud-gas mixing device 10 is added in liquid after desulfurization process
Doctor solution is mixed with biogas, is realized the microvesicle of biogas, can be installed between doctor solution storage pool 70 and Liqiud-gas mixing device 10
Buffer stable-pressure device, buffering stable-pressure device can be pressure reducing valve, can be surge tank, enable doctor solution it is stable enter gas
In liquid mixing arrangement 10.
In the specific implementation process of some embodiments of the invention, methane-desulfurizing device 100 can also include at least two
Valve 61 and two flowmeters 62, at least one valve 61 and a flowmeter 62 can be located at biogas storage tank 60 and gas-liquid is mixed
It attaches together and sets between 10, for adjusting the flow for entering the biogas of Liqiud-gas mixing device 10, the flow of biogas is shown, just
It is operated in control, at least one valve 61 and a flowmeter 62 can be located at doctor solution storage pool 70 and Liqiud-gas mixing device 10
Between, for adjusting the flow of doctor solution, the flow of doctor solution is shown, convenient for control operation.
In the specific implementation process of other embodiments of the invention, methane-desulfurizing device 100 can also include circulating pump
80 and control valve 81, wherein circulating pump 80 can be connected together with gas-liquid separation pond 30 and regenerating unit 50 respectively, be used for
Sulfur-bearing doctor solution in gas-liquid separation pond 30 is pumped into regenerating unit 50, control valve 81 can be located at circulating pump 80 and gas-liquid
Sulfur-bearing doctor solution between separate tank 30 for adjusting in gas-liquid separation pond 30 enters the flow of regenerating unit 50.
Biogas microvesicle can be increased biogas and doctor solution by methane-desulfurizing device 100 according to an embodiment of the present invention
Contact area improves desulfuration efficiency, and metal phthalocyanine catalyst, which is loaded to, can reduce catalyst loss on titanium foam, mention
High catalyst utilization rate increases reaction contact area, is conducive to desulfurization regeneration, improves regeneration efficiency, and apparatus structure letter
It is single, it is easy to accomplish.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, it can also make several improvements and retouch, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (15)
1. a kind of biogas desulfurization method, which comprises the following steps:
S1, biogas is sufficiently mixed with doctor solution make the biogas microvesicle after carry out desulfurization process and react；
S2, the mixed liquor progress gas-liquid separation of biogas and doctor solution after desulfurization process is obtained into desulfurization biogas and sulfur-bearing desulfurization
Liquid；
S3, purified treatment is dried in the obtained desulfurization biogas；
S4, the obtained sulfur-bearing doctor solution is subjected to desulfurization regeneration processing under the action of metal phthalocyanine catalyst and oxygen,
Sulfur-bearing doctor solution after regeneration treatment remakes doctor solution after separating treatment and recycles.
2. biogas desulfurization method according to claim 1, which is characterized in that in the step S1, in the doctor solution
Mixture including sodium carbonate or sodium carbonate and sodium bicarbonate.
3. biogas desulfurization method according to claim 1, which is characterized in that the step S4 the following steps are included:
S41, the sulfur-bearing doctor solution is added in the regenerating unit equipped with metal phthalocyanine catalyst, is led in Xiang Suoshu regenerating unit
Enter oxygen and carry out desulfurization regeneration processing, generates elemental sulfur；
S42, it the elemental sulfur of generation is isolated from the sulfur-bearing doctor solution after the regeneration treatment respectively obtains elemental sulfur
With liquid after desulfurization process, liquid is recycled as doctor solution after the desulfurization process.
4. biogas desulfurization method according to claim 1, which is characterized in that in the step S4, the metal phthalocyanine
Catalyst is the phthalocyanine cobalt catalyst loaded on titanium foam.
5. biogas desulfurization method according to claim 4, which is characterized in that the phthalocyanine cobalt catalyst is loaded to titanium
Belong to foam on method the following steps are included:
Glacial acetic acid and ethanol solution are prepared, Cobalt Phthalocyanine and dinethylformamide and stirring and dissolving is added into solution respectively, then
It is slowly added to sodium hydroxide solution, until raw material is completely dissolved, then titanium foam is added into mixed solution；
Solution equipped with titanium foam is placed in hydrothermal reaction kettle reaction 4h at a temperature of 250 DEG C by ultrasonic treatment to obtain
To treated titanium foam；
It takes out treated the titanium foam and is dried and is sintered, obtain the Cobalt Phthalocyanine loaded on titanium foam
Catalyst.
6. biogas desulfurization method according to claim 5, which is characterized in that the phthalocyanine cobalt catalyst is being loaded to titanium
In method on metal foam, the glacial acetic acid, ethyl alcohol, Cobalt Phthalocyanine, dinethylformamide and titanium foam mass ratio
For 5:30:1:2.5:4.
7. biogas desulfurization method according to claim 5, which is characterized in that treated the titanium foam into
When row sintering, first by treated the titanium foam 260 DEG C at a temperature of be sintered 1h, then 350 DEG C at a temperature of burn
Tie 2h.
8. a kind of methane-desulfurizing device characterized by comprising
Liqiud-gas mixing device, the Liqiud-gas mixing device are respectively provided with the feed inlet that biogas and doctor solution is added and discharge natural pond
The discharge port of the mixed liquor of gas and doctor solution, the Liqiud-gas mixing device are used to mix the biogas and the doctor solution being added
And by the biogas microvesicle；
Reactor, the import of the reactor are connected with the discharge port of the Liqiud-gas mixing device to mix the gas-liquid
The mixed liquor in setting is attached together to be added in the reactor and carry out desulphurization reaction；
Gas-liquid separation pond, the gas-liquid separation pond and the reactor are connected with by the mixed liquor after reacting in the reactor
It is transferred in the gas-liquid separation pond and carries out gas-liquid separation and obtain desulfurization biogas and sulfur-bearing doctor solution；
Dry decontamination device, the dry decontamination device are connected for containing described in simultaneously dry decontamination with the gas-liquid separation pond
The desulfurization biogas isolated in gas-liquid separation pond；
Regenerating unit, the regenerating unit are connected with the Liqiud-gas mixing device and the gas-liquid separation pond respectively, for pair
The sulfur-bearing doctor solution isolated in the gas-liquid separation pond is regenerated, after the elemental sulfur generated in regeneration is isolated
Liquid and being transferred in the Liqiud-gas mixing device as doctor solution is mixed with the biogas after to desulfurization process.
9. methane-desulfurizing device according to claim 8, which is characterized in that the Liqiud-gas mixing device is gas-liquid mixed
Pump, the reactor are baffled reactor.
10. methane-desulfurizing device according to claim 8, which is characterized in that be equipped with carried metal in the regenerating unit
The titanium foam of phthalocyanine catalyst.
11. methane-desulfurizing device according to claim 8, which is characterized in that the bottom of the regenerating unit be taper and
It is equipped with the sulphur outlet for the elemental sulfur generated to be discharged in the bottom, controlled valve is equipped in the sulphur outlet and passes through institute
State the switch that controlled valve controls the sulphur outlet.
12. methane-desulfurizing device according to claim 8, which is characterized in that further include:
Bubbler, the bubbler are arranged in the regenerating unit for being passed through air or oxygen to the sulfur-bearing doctor solution.
13. methane-desulfurizing device according to claim 8, which is characterized in that further include:
Biogas storage tank, the biogas storage tank are connected with the Liqiud-gas mixing device, for storing the biogas and by institute
It states biogas and the Liqiud-gas mixing device is added；
Doctor solution storage pool, the doctor solution storage pool are connected with the Liqiud-gas mixing device and the regenerating unit respectively,
For store regenerated in the regenerating unit after liquid and institute is added in liquid after the desulfurization process after the obtained desulfurization process
Liqiud-gas mixing device is stated as doctor solution to mix with the biogas.
14. methane-desulfurizing device according to claim 13, which is characterized in that further include:
At least two valves and two flowmeters, at least one described valve and a flowmeter are located at the biogas storage
For adjusting the flow into the biogas of the Liqiud-gas mixing device between tank and the Liqiud-gas mixing device, at least one
The valve and a flowmeter are located between the doctor solution storage pool and the Liqiud-gas mixing device for adjusting institute
State the flow of doctor solution.
15. methane-desulfurizing device according to claim 8, which is characterized in that further include:
Circulating pump, the circulating pump are connected with the gas-liquid separation pond and the regenerating unit respectively, for dividing the gas-liquid
The regenerating unit is pumped into from the sulfur-bearing doctor solution in pond；
Control valve, the control valve are located between the circulating pump and the gas-liquid separation pond for adjusting the gas-liquid point
From the flow that the sulfur-bearing doctor solution in pond enters the regenerating unit.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080261801A1 (en) * | 2004-12-24 | 2008-10-23 | Johnson Matthey Public Limited Company | Methods of Regenerating a Nox Absorbent |
| CN102133547A (en) * | 2011-03-02 | 2011-07-27 | 华南理工大学 | Ozone treatment regeneration method and device for vanadium titanium-based flue gas denitration catalyst |
| US20120222555A1 (en) * | 2011-03-01 | 2012-09-06 | Exxonmobil Research And Engineering Company | Gas Purification Process Utilizing Engineered Small Particle Adsorbents |
| CN103980971A (en) * | 2014-05-29 | 2014-08-13 | 湖南和道资源科技有限公司 | Methane treatment method and methane treatment system |
| AU2013281028A1 (en) * | 2012-06-29 | 2014-10-23 | Dow Global Technologies Llc | Aqueous alkanolamine solution and process for the removal of H2S from gaseous mixtures |
| 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 |
-
2017
- 2017-12-19 CN CN201711377764.2A patent/CN109929636B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080261801A1 (en) * | 2004-12-24 | 2008-10-23 | Johnson Matthey Public Limited Company | Methods of Regenerating a Nox Absorbent |
| US20120222555A1 (en) * | 2011-03-01 | 2012-09-06 | Exxonmobil Research And Engineering Company | Gas Purification Process Utilizing Engineered Small Particle Adsorbents |
| CN102133547A (en) * | 2011-03-02 | 2011-07-27 | 华南理工大学 | Ozone treatment regeneration method and device for vanadium titanium-based flue gas denitration catalyst |
| AU2013281028A1 (en) * | 2012-06-29 | 2014-10-23 | Dow Global Technologies Llc | Aqueous alkanolamine solution and process for the removal of H2S from gaseous mixtures |
| CN103980971A (en) * | 2014-05-29 | 2014-08-13 | 湖南和道资源科技有限公司 | Methane treatment method and methane treatment system |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 王录才、王芳著: "《泡沫金属制备、性能及应用》", 31 October 2012 * |
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