CN101984026B - Integrated methane biological desulphurization device - Google Patents
Integrated methane biological desulphurization device Download PDFInfo
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- CN101984026B CN101984026B CN 201010535116 CN201010535116A CN101984026B CN 101984026 B CN101984026 B CN 101984026B CN 201010535116 CN201010535116 CN 201010535116 CN 201010535116 A CN201010535116 A CN 201010535116A CN 101984026 B CN101984026 B CN 101984026B
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- thionizer
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- pipe
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000007921 spray Substances 0.000 claims abstract description 27
- 230000000050 nutritive effect Effects 0.000 claims description 43
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 37
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 24
- 239000000945 filler Substances 0.000 claims description 23
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 21
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 21
- 239000004571 lime Substances 0.000 claims description 21
- 238000012546 transfer Methods 0.000 claims description 21
- 241000894006 Bacteria Species 0.000 claims description 19
- 238000005273 aeration Methods 0.000 claims description 16
- 230000003009 desulfurizing effect Effects 0.000 claims description 16
- 238000005276 aerator Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 10
- 238000001802 infusion Methods 0.000 claims description 9
- 238000011067 equilibration Methods 0.000 claims description 8
- 238000002955 isolation Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract 4
- 238000006477 desulfuration reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- -1 temperature Chemical compound 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000031018 biological processes and functions Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241001554087 Thiobacterium Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000013028 medium composition Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention discloses an integrated methane biological desulphurization device which comprises a tower body composed of an upper desulphurization tower (3) and a lower desulphurization tower (16) which are isolated from each other, a spray system and a reflux system, wherein, the top of the upper desulphurization tower (3) is equipped with a methane outlet (1); the spray system comprises a spray header (2) arranged at the top half of an inner chamber of the upper desulphurization tower (3) and a delivery pipe (23) arranged outside the tower body; two ends of the delivery pipe (23) are respectively communicated with the spray header (2) in the upper desulphurization tower (3) and an inner chamber of the lower desulphurization tower (16); the delivery pipe (23) is equipped with a circulating pump (17); and the reflux system comprises a reflux pipe (19) arranged outside the tower body, and two ends of the reflux pipe (19) are respectively communicated with the bottom of the inner chamber of the upper desulphurization tower (3) and the inner chamber of the lower desulphurization tower (16). The integrated methane biological desulphurization device has the characteristics of being safe and efficient and being capable of monitoring technological parameters in real time and the like.
Description
Technical field
The present invention relates to a kind of safely and efficiently Integral biological methane desulfurizer, belong to the biogas desulfurization field of engineering technology.
Background technology
In the biogas that the agricultural organic waste anaerobically fermentings such as feces of farm and crop material produce, except mainly containing the methane and carbon dioxide, also has the hydrogen sulfide of trace.Hydrogen sulfide is a kind of high pungency severe toxicity gas, under aerobic and wet heat condition, not only can cause equipment and corrosion of piping, but also can pollute atmospheric environment, the serious threat personnel safety.Therefore, Environmental Protection in China standard strict regulation: when utilizing biogas energy, the content of hydrogen sulfide must not surpass 20mg/m in the biogas
3In the undressed biogas, the concentration of hydrogen sulfide is generally 1～12g/m
3, be higher than the regulation of Environmental Protection in China standard far away, therefore, removing of hydrogen sulfide becomes the biogas use procedure, a requisite link in the especially marsh gas power generation engineering.
At present, the method for biogas desulfurization has chemical method, physico-chemical process and biological process etc.There are the shortcomings such as working cost is high, investment is large, generation secondary pollution in traditional physico-chemical processes, is difficult to large-scale promotion application.And the biological process that rose in recent years to be metabolism by desulfurizing bacteria be converted into elemental sulfur with hydrogen sulfide, because it does not need catalyzer and oxygenant (aerobic gas), need not process chemical sludge, less contamination, less energy-consumption, high-level efficiency, the advantage such as recyclable elemental sulfur and more being concerned.But the biological desulphurization method must be built an adapt circumstance to thiobacterium, and the factors such as control pH value, dissolved oxygen, temperature, hydrogen sulphide load can guarantee that just it has higher biological activity, to reach best sweetening effectiveness.
Owing to need oxygen in the metabolic process of desulfurization bacterium, and biogas is inflammable gas, directly mixes with oxygen, has the potential safety hazard of blasting.Such as Chinese patent disclosed " methane bio-desulfurization device " (CN 200710067269.1), air enters after same import directly mixes with biogas, has potential safety hazard.In addition, the control of dissolved oxygen requires very highly in the metabolic process of desulfurization bacterium, too much or very fewly all can have a strong impact on sweetening effectiveness.How to control rational aeration rate, making the final product behind the biological desulphurization is elemental sulfur, is the another key point of methane bio-desulfurization technology.In order accurately to control dissolved oxygen content, Chinese patent disclosed " methane bio-desulfurization device " (CN 200910162260.8), the settling bowl five equilibrium of desulfurization pond, elemental sulfur under biological desulphurization tower, the nutritive medium is located in the device that is arranged in parallel, but there are the defectives such as Whole Equipment is complicated, occupied ground is large in it.Prior art is mainly single aerobic method biological desulphurization, practical sulphur removal efficient is difficult to reach more than 95%, and along with the variation of hydrogen sulfide in methane load, the parameters such as sweetening process dissolved oxygen content, pH value are extremely unstable, and the hydrogen sulfide content after the desulfurization in the biogas is difficult to the stable 20mg/m that is controlled at
3Below.
Summary of the invention
But the technical problem to be solved in the present invention provides a kind of Integral biological methane desulfurizer of safe, efficient, processing parameter Real Time Monitoring.
In order to solve the problems of the technologies described above, the invention provides Integral biological methane desulfurizer, comprise tower body and sprinkling system and return-flow system that upper thionizer and lower thionizer by mutual isolation form; Top at upper thionizer arranges methane outlet, sprinkling system comprises the spray header that is arranged at the thionizer inner chamber first half and is positioned at the outer transfer lime of tower body, the two ends of transfer lime respectively with upper thionizer in spray header and with the intracavity inter-connection of lower thionizer, be provided with recycle pump at transfer lime; Return-flow system comprises and is positioned at the outer return line of tower body, the two ends of return line respectively with the bottom of upper thionizer inner chamber and with the intracavity inter-connection of lower thionizer.
Improvement as Integral biological methane desulfurizer of the present invention: the filler that contains desulfurizing bacteria is set in the inner chamber of upper thionizer, and filler is positioned at the below of spray header; Also be respectively equipped with the hot-water coil pipe, biogas inlet pipe and the biogas gas distribution pipe that are arranged in order from top to bottom below filler in the inner chamber of upper thionizer, the biogas inlet pipe is connected with the biogas gas distribution pipe; The entrance end of the entrance end of hot-water coil pipe and biogas inlet pipe all passes through the outside that is positioned at thionizer behind the sidewall of thionizer hermetically, is provided with bleed valve on the elemental sulfur with the intracavity inter-connection of upper thionizer at the sidewall of upper thionizer; Bleed valve is near the bottom of upper thionizer on the elemental sulfur.
Further improvement as Integral biological methane desulfurizer of the present invention: the entrance end of liquid-inlet pipe links to each other with the nutritive medium fluid infusion case sealing that is positioned at lower thionizer outside, the exit end of liquid-inlet pipe passes through the inner chamber that is arranged in lower thionizer behind the sidewall of lower thionizer hermetically, is provided for controlling the float valve of liquid-inlet pipe conducting at the exit end of liquid-inlet pipe; Be provided with the dish type aerator with aeration head in lower thionizer, float valve is positioned at the top of dish type aerator; Be positioned at the blast pipe of lower thionizer outside and be connected with aeration head on the dish type aerator, at blast pipe intake valve is set; In the bottom of lower thionizer bleed valve under the elemental sulfur with the intracavity inter-connection of lower thionizer is set.
Further improvement as Integral biological methane desulfurizer of the present invention: in the upper end of return line lower curved elbow is set, elbow is connected with the bottom of upper thionizer inner chamber; At return line the equilibration tube that the inner chamber make return line is connected with ambient atmosphere is set.
Further improvement as Integral biological methane desulfurizer of the present invention: vapor pipe is connected with the first half of lower thionizer inner chamber.
Further improvement as Integral biological methane desulfurizer of the present invention: on transfer lime, be respectively equipped with strainer, recycle pump and variable valve according to the flow direction of carrying liquid in pipe, the entrance end of transfer lime and the lower thionizer intracavity inter-connection that is positioned at dish type aerator below; Lower end at strainer arranges bleed valve.
Further improvement as Integral biological methane desulfurizer of the present invention: the upper/lower terminal at filler respectively arranges the data acquisition unit I that a cover is comprised of temperature sensor and pH value sensor; Be provided for detecting respectively the data acquisition unit II of concentration of hydrogen sulfide and flow in the ingress of biogas inlet pipe; Be provided for detecting respectively the gas concentration collector of concentration of hydrogen sulfide and oxygen concentration at the methane outlet place, in the inner chamber of lower thionizer, be provided for detecting the data acquisition unit III of solution temperature, pH value and dissolved oxygen.
The present invention compares the beneficial effect that has with background technology:
(1) thionizer, nutritive medium spray and becoming one of return-flow system up and down, processing and easy for installation, and the occupied ground area is little, is conducive to apply.
(2) biogas and air enter respectively in thionizer and the lower thionizer, and both are spaced from each other, guarantee the fully isolated of biogas and air, have avoided the hidden danger that oxygen and biogas directly mix existence in the prior art.In addition, the equilibration tube that is communicated with it is set on return line, can prevent siphonage, guarantee that the solution in the upper thionizer remains at certain liquid level, and can all not be back in the lower thionizer, the elbow of return line is immersed under the liquid level all the time, plays the water seal effect, biogas can not be communicated with extraneous air in the tower, has guaranteed the safe operation of methane bio-desulfurization.
(3) carry out the biological desulphurization of biogas in the thionizer, under the effect of packing area desulfurizing bacteria, hydrogen sulfide in methane is converted into elemental sulfur, simultaneously, but also absorption portion hydrogen sulfide of the spray liquid of packing area, and biogas passes in the solution, but solution absorption portion hydrogen sulfide, solution enters the aerobe desulfurization that circulates of lower thionizer by return line, thereby has improved the efficient of methane bio-desulfurization, and the hydrogen sulfide in methane clearance is greater than 95%.Hydrogen sulfide content after the desulfurization in the biogas can be stablized and is controlled at 20mg/m
3Below.
(4) utilize hot-water coil pipe that the biogas that enters cold season in the tower is heated, guarantee the temperature that biological desulphurization is suitable, avoid directly nutritive medium being heated and make the uncontrollable situation of dissolved oxygen content due on the low side.
(5) utilize the interior dissolved oxygen concentration of data acquisition unit III assaying reaction liquid in the lower thionizer, regulate aeration rate by the intake valve of regulating on the blast pipe, make Dissolved Oxygen concentration Control between 0.8～1.0mg/L, impel hydrogen sulfide to transform to elemental sulfur, and prevent from the acidifying of reaction solution from having realized the efficient operation of methane bio-desulfurization.
(6) installation by the different positions sensor, processing parameter and sweetening effectiveness energy Real-Time Monitoring and the controls such as the pH value in the sweetening process, dissolved oxygen, temperature, hydrogen sulphide load, build an adapt circumstance to desulfurizing bacteria, guarantee that it has higher biological activity, to reach best sweetening effectiveness.
(7) arranging of liquid-inlet pipe and float valve can be realized automatically replenishing of nutritive medium, makes the interior nutritive medium liquid level of lower thionizer keep stable; Nutritive medium in the lower thionizer can be discharged by the bleed valve of strainer lower end, replenishes new nutritive medium by nutritive medium fluid infusion case and liquid-inlet pipe, can realize the renewal of nutritive substance in the tower.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is the structural representation of Integral biological methane desulfurizer of the present invention;
Among Fig. 1:
1, methane outlet, 2, spray header, 3, upper thionizer, 4, hot-water coil pipe, 5, the biogas inlet pipe, 6, the biogas gas distribution pipe, 7, nutritive medium fluid infusion case, 8, liquid-inlet pipe, 9, blast pipe, 10, intake valve, 11, vision slit, 12, aeration head, 13, bleed valve under the elemental sulfur, 14, bleed valve, 15, strainer, 16, lower thionizer, 17, recycle pump, 18, variable valve, 19, return line, 20, vapor pipe, 21, bleed valve on the elemental sulfur, 22, equilibration tube, 23, transfer lime, 24, filler, 25, elbow, 26, float valve, 27, the dish type aerator;
101, data acquisition unit I, 102, data acquisition unit II, 103, the gas concentration collector, 104, the data acquisition unit III.
Embodiment
Fig. 1 has provided a kind of Integral biological methane desulfurizer, comprises tower body and sprinkling system and return-flow system that upper thionizer 3 and lower thionizer 16 by mutual isolation form.Rely on sprinkling system and return-flow system, the liquid in upper thionizer 3 and the lower thionizer 16 can circulate mutually.Upper thionizer 3 is positioned at the top of lower thionizer 16, and lower thionizer 16 is used for the biological desulphurization of biogas, and upper thionizer 3 is used for the biological desulphurization of biogas.
At the top of upper thionizer 3 methane outlet 1 is set; The filler 24 that contains desulfurizing bacteria is set in the inner chamber of upper thionizer 3, and this filler 24 links to each other with the internal surface of upper thionizer 3 sidewalls, thereby could discharge from methane outlet 1 after making biogas must pass through the processing of filler 24.Filler 24 is optional to be the soft-filler of basic material in order to the fine synthetic fibre of hydroformylation.
Sprinkling system comprises the spray header 2 that is arranged at the thionizer 3 inner chamber first halves and is positioned at the outer transfer lime 23 of tower body that this spray header 2 is positioned at the top of filler 24.In the inner chamber of upper thionizer 3, also be respectively equipped with hot-water coil pipe 4, biogas inlet pipe 5 and the some biogas gas distribution pipes 6 that are parallel to each other; Hot-water coil pipe 4, biogas inlet pipe 5 and biogas gas distribution pipe 6 being arranged in order in the below of filler 24 from top to bottom; The top of biogas gas distribution pipe 6 be connected with biogas inlet pipe 5 (biogas gas distribution pipe 6 and biogas inlet pipe 5 is mutually vertical).The entrance end of the entrance end of hot-water coil pipe 4 and biogas inlet pipe 5 all passes through the outside that is positioned at thionizer 3 behind the sidewall of thionizer 3 hermetically.Be provided with bleed valve 21 on the elemental sulfur with the intracavity inter-connection of upper thionizer 3 at the sidewall of upper thionizer 3, bleed valve 21 is positioned at the below of biogas gas distribution pipe 6 bottoms on this elemental sulfur; That is, the bottom of bleed valve 21 close upper thionizers 3 on the elemental sulfur.Hot-water coil pipe 4 is mainly used in the biogas that enter in the upper thionizer 3 being heated during low temperature cold season.
At lower thionizer 16 outer setting nutritive medium fluid infusion casees 7 be positioned at liquid-inlet pipe 8 below the nutritive medium fluid infusion case 7, the entrance end of liquid-inlet pipe 8 links to each other with the bottom end seal of nutritive medium fluid infusion case 7, the exit end of liquid-inlet pipe 8 passes through the inner chamber that is arranged in lower thionizer 16 behind the sidewall of lower thionizer 16 hermetically, is provided for controlling the float valve 26 of liquid-inlet pipe 8 conductings at the exit end of liquid-inlet pipe 8; Vision slit 11 also is set, by the nutritive medium in thionizer 16 inner chambers under vision slit 11 Observables on the sidewall of lower thionizer 16.
Be provided with the dish type aerator 27 with several aeration heads 12 in lower thionizer 16, dish type aerator 27 is positioned at the below of float valve 26; The blast pipe 9 that is positioned at lower thionizer 16 outsides passes through hermetically behind the sidewall of lower thionizer 16 with aeration head 12 on the dish type aerator 27 and is connected, and at blast pipe 9 intake valve 10 is set, and intake valve 10 is used for regulating the aeration rate of air.In the bottom of lower thionizer 16 bleed valve 13 under the elemental sulfur with the intracavity inter-connection of lower thionizer 16 is set.
For the ease of precipitation and the discharging of elemental sulfur, back taper can be arranged in the bottom of lower thionizer 16, and in like manner, upper thionizer 3 also can be arranged to back taper.
Flow direction according to transfer lime 23 interior liquid on transfer lime 23 is respectively equipped with strainer 15, recycle pump 17 and variable valve 18, the entrance end of transfer lime 23 and the intracavity inter-connection that is positioned at the lower thionizer 16 of dish type aerator 27 belows; The exit end of transfer lime 23 is connected with spray header 2 in the upper thionizer 3.In the lower end of strainer 15 bleed valve 14 is set; When opening bleed valve 14, nutritive medium in the lower thionizer 16 is discharged from bleed valve 14, at this moment, the float valve 26 at the exit end place of liquid-inlet pipe 8 is opened automatically, thereby make liquid-inlet pipe 8 be in conducting state, new nutritive medium in the nutritive medium fluid infusion case 7 replenishes by liquid-inlet pipe 8 and enters in the lower thionizer 16, can realize the renewal of nutritive substance in the tower.
Return-flow system comprises the return line 19 that is positioned at outside the tower body, and return line 19 is by two level pipes and a straight tube are formed by connecting up and down.In the upper end of return line 19 a lower curved elbow 25 is set, that is, elbow 25 links to each other with the upper level pipe of return line 19; This elbow 25 is connected with the bottom of upper thionizer 3 inner chambers; The intracavity inter-connection of the lower end of return line 19 and lower thionizer 16 (that is, the intracavity inter-connection of the lower level pipe of return line 19 and lower thionizer 16).The equilibration tube 22 that the inner chamber that makes return line 19 is connected with ambient atmosphere is set at the upper level pipe place of return line 19.
Sidewall at lower thionizer 16 is provided with vapor pipe 20, the intracavity inter-connection of the first half of this vapor pipe 20 and lower thionizer 16.
Be the processing parameters such as pH value, dissolved oxygen, temperature, hydrogen sulphide load in the accurate control desulfurization operation process, at the upper/lower terminal of filler 24 the data acquisition unit I101 that a cover is comprised of temperature sensor and pH value sensor be set respectively; Be provided for detecting respectively the data acquisition unit II102 of concentration of hydrogen sulfide and flow in the ingress of biogas inlet pipe 5; Be provided for detecting respectively the gas concentration collector 103 of concentration of hydrogen sulfide and oxygen concentration at methane outlet 1 place, the data acquisition unit III 104 of temperature, pH value and the dissolved oxygen of thionizer 16 interior liquid under in the inner chamber of lower thionizer 16, being provided for detecting.
During the actual use of Integral biological methane desulfurizer of the present invention, liquid level of solution in the upper thionizer 3 and the distance of upper thionizer 3 bottom surfaces are 20-30cm, the bottom surface 5cm of the upper thionizer 3 of port distance of the elbow 25 on the return line 19, namely, elbow 25 ports on the return line 19 immerse the following 15-25cm of this liquid level of solution, make elbow 25 immerse end and are in all the time the water seal state.Biogas gas distribution pipe 6 immerses below the liquid level of solution, and the bottom of biogas gas distribution pipe 6 is apart from liquid level 10-15cm, just rises to filler 24 after making biogas through solution (water-bath).The height of lower thionizer 16 end faces of lower thionizer 16 interior liquid level distances is 20-30cm, and at this liquid level position, the float valve 26 on the liquid-inlet pipe 8 is in closing condition, and the exit end of liquid-inlet pipe 8 is higher than this liquid level 15-25cm; The port of vapor pipe 20 is higher than this liquid level 15-25cm, and the unnecessary gas in lower thionizer 16 inner chambers can be discharged by vapor pipe 20.Aeration head 12 on the dish type aerator 27 is positioned under the liquid level of lower thionizer 16, and the lower end of return line 19 (the lower level pipe of return line 19) passes in the liquid of lower thionizer 16 interior aeration heads 12 tops.By the size of intake valve 10 adjusting blast pipes 9 interior air outputs, thus control air aeration amount, and the dissolved oxygen concentration that makes the data acquisition unit III record lower thionizer 16 interior liquid maintains 0.8-1.0mg/L.The variable valve 18 that arranges on the transfer lime 23 is used for regulating nutritive medium by the spray flux size of spray header 2 and the vapour-liquid ratio (being the ratio P of biogas and nutritive medium) of upper thionizer 3 inner chambers.Intake valve 10 all can link to each other with a frequency-variable controller with variable valve 18, to realize automatic adjusting and the control of processing parameter.In the present invention, the prescription of nutritive medium composition for example can be (g/L): NaS
2O
35H
2O, 5.0g; K
2HPO
4, 2.0g; KNO
3, 2.0g; MgSO
47H
2O, 0.6g; NH
4CI, 0.5g; FeSO
47H
2O, 0.01g; All the other are water, and generally regulating the pH value is 7.5～8.0.
During the actual use of the present invention, thereby placing in advance the biofilm cultivation that desulfurizing bacteria carries out desulfurizing bacteria in filler 24, for example is aerobic desulfurizing bacteria (sulfur-oxidizing bacteria), and this is routine techniques.Contain the inoculum of aerobic desulfurizing bacteria in lower thionizer 16 interior inoculations, for example take from the Wastewater from Pig Farm enrichment and active sludge (including aerobic desulfurizing bacteria); It is immersed in the nutritive medium.
Principle of work of the present invention and process are as follows:
(1) methane bio-desulfurization of upper thionizer 3:
Liquid (mainly comprising nutritive medium) in the lower thionizer 16 enters in the spray header 2 by transfer lime 23 (recycle pump 17 provides power), then spray on the filler 24 that hangs from spray header 2 from top to down, in the liquid (mainly comprising nutritive medium) of biogas through biogas gas distribution pipe 6 enters upper thionizer 3 in that flows into from biogas inlet pipe 5, just rise to filler 24 after making biogas pass through liquid (water-bath).
Therefore, in the conversion zone of upper thionizer 3, the hydrogen sulfide containing biogas that enters from the bottom is constantly upwards carried, with the liquid inverse that contains alkaline nutritive medium of downward spray to contacting, hydrogen sulfide is dissolved in basic solution.At this moment, the desulfurizing bacteria in the filler 24 will further utilize the residue dissolved oxygen in the nutritive medium, impel hydrogen sulfide to be converted into elemental sulfur.Hydrogen sulfide in the reaction solution enters lower thionizer 16 in company with reaction solution by return line 19, carries out the recycled biogas biological desulphurization, and hydrogen sulfide is further removed and produced elemental sulfur.Because the contained dissolved oxygen content of spray liquid lower (being remaining behind lower thionizer 16 internal reactions) in the upper thionizer 3, and under the effect of desulfurizing bacteria, transform rapidly, prevent the release of dissolved oxygen, avoided mixing of biogas and oxygen, realized the safe operation of methane bio-desulfurization.The elemental sulfur of upper thionizer 3 interior formation can be got rid of by bleed valve on the elemental sulfur 21.The biogas that removes behind the hydrogen sulfide is discharged from methane outlet 1.
(2) methane bio-desulfurization of lower thionizer:
Be provided with the data acquisition unit II for detection of desulphurization reaction liquid temp, pH value and dissolved oxygen in the lower thionizer 16; Thereby measure the dissolved oxygen concentration in the desulphurization reaction liquid, and by intake valve 10 control air aeration amounts, the interior dissolved oxygen concentration of desulphurization reaction liquid is maintained between 0.8～1.0mg/L, impel hydrogen sulfide under the effect of desulfurizing bacteria, to transform to elemental sulfur, and prevent the acidifying of desulphurization reaction liquid.The main reaction that occurs in the liquid phase is: 2HS
-+ O
2→ 2S+2OH
-Excessive air is then discharged outside the lower thionizer 16 by vapor pipe 20, has avoided oxygen to enter possibility in the thionizer 3 fully, thereby has got rid of the hidden danger that oxygen and biogas mixed occurrence explode.
(3) sprinkling system.The pH of nutrient solution value is controlled between 7.5～8.0, when impelling the desulfurizing bacteria growth, also can strengthen nutritive medium to the absorption of hydrogen sulfide in gas phase gas.Liquid (mainly comprising nutritive medium) in the lower thionizer 16 pumps in the spray header 2 along transfer lime 23 by recycle pump 17, realizes the even sprinkling of nutritive medium through spray header 2; The size of spray flux also can make variable valve 18 link to each other with frequency transformer by variable valve 18 manual shift, realizes automatic adjusting and the control of the processing parameters such as vapour-liquid ratio.
(4) return-flow system.When the liquid level in the upper thionizer 3 was higher than the upper level pipe of return line 19, the solution (being hydrogen sulfide containing reaction solution) that is absorbed with hydrogen sulfide in the upper thionizer 3 entered in the lower thionizer 16 by return line 19; Be provided with the equilibration tube 22 that is communicated with it on the return line 19, when the liquid level in the return line 19 is lower than return line 19 with handing-over mouth that equilibration tube 22 is communicated with, can prevent siphonage, thereby guarantee that the solution in the upper thionizer 3 remains at certain liquid level, can all not be back in the lower thionizer 16; Elbow 25 on the return line 19 is immersed under the liquid level all the time, plays the water seal effect, and the biogas in the thionizer 3 can not flowed to outside the tower by equilibration tube 22, and the tower outer air can not enter in the thionizer 3 yet, has guaranteed the safe operation of methane bio-desulfurization.
(5) nutritive medium replenishes and renewal.The purpose that liquid-inlet pipe 8 and float valve 26 are set is: make lower thionizer 16 interior nutritive medium liquid levels keep stable, float valve 26 is opened when liquid level is lower than certain altitude, can realize the automatically additional of nutritive medium.Namely, when the nutritive medium in the thionizer 16 is discharged by the bleed valve 14 of strainer 15 instantly, liquid level in the lower thionizer 16 descends, float valve 26 is opened, liquid-inlet pipe 8 is in conducting state, the new nutritive medium of nutritive medium fluid infusion case 7 adds in the lower thionizer 16 by liquid-inlet pipe 8, thereby realizes the renewal of lower thionizer 16 interior nutritive substances.The inoculum that strainer 15 can effectively be intercepted in the lower thionizer 16 flows in the transfer lime 23.When needs replenished new nutritive medium, the bleed valve 14 of opening strainer 15 got final product.
(6) elemental sulfur discharging and collection.Hydrogen sulfide in the biogas forms elemental sulfur through the effect of aerobic desulfurizing bacteria.The more general mud of sulfur-bearing sludge density is large, under action of gravity, sulfur-bearing mud is precipitated to the back taper bottom of thionizer 3 bottoms and lower thionizer 16 gradually, finally from the elemental sulfur under bleed valve 21 and the elemental sulfur bleed valve 13 discharge, reach the purpose that reclaims elemental sulfur.
(7) parameter measure and control.Upper/lower terminal at filler 24 respectively arranges a cover by the data acquisition unit I101 that temperature sensor and pH value sensor form, and enables hot-water coil pipe 4 and heat when temperature is lower than 20 ℃, the pH value that the pH value is then regulated spray liquid unusually.Be provided for detecting respectively the data acquisition unit II of concentration of hydrogen sulfide and flow in the ingress of biogas inlet pipe 5, be used for feedback control recycle pump 17 and variable valve 18, regulate vapour-liquid ratio.Be provided for detecting respectively the gas concentration collector of concentration of hydrogen sulfide and oxygen concentration at methane outlet 1 place, when methane outlet 1 place's concentration of hydrogen sulfide exceeds standard, then need comprehensive adjustment nutritive medium parameter or upgrade nutritive medium, when oxygen concentration exceeds standard, then must carry out repair and maintenance to equipment.In the inner chamber of lower thionizer 16, be provided for detecting the data acquisition unit III of temperature, pH value and the dissolved oxygen of desulphurization reaction liquid, temperature is worked as abnormal DO as the reference value that affects dissolved oxygen content, then needs to regulate intake valve 10, control aeration rate, when the pH value, consider to regulate the nutritive medium parameter.
At last, it is also to be noted that what more than enumerate only is a specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. Integral biological methane desulfurizer is characterized in that: comprise tower body and sprinkling system and return-flow system that upper thionizer (3) and lower thionizer (16) by mutual isolation form; At the top of upper thionizer (3) methane outlet (1) is set, described sprinkling system comprises the spray header (2) that is arranged at thionizer (3) the inner chamber first half and is positioned at the outer transfer lime (23) of tower body, the two ends of described transfer lime (23) respectively with upper thionizer (3) in spray header (2) and with the intracavity inter-connection of lower thionizer (16), be provided with recycle pump (17) at transfer lime (23); Described return-flow system comprises and is positioned at the outer return line (19) of tower body, the two ends of described return line (19) respectively with the bottom of upper thionizer (3) inner chamber and with the intracavity inter-connection of lower thionizer (16);
The filler (24) that contains desulfurizing bacteria is set in the inner chamber of thionizer on described (3), and described filler (24) is positioned at the below of spray header (2); Also be respectively equipped with the hot-water coil pipe (4), biogas inlet pipe (5) and the biogas gas distribution pipe (6) that are arranged in order from top to bottom in filler (24) below in the inner chamber of upper thionizer (3), described biogas inlet pipe (5) is connected with biogas gas distribution pipe (6); The entrance end of the entrance end of described hot-water coil pipe (4) and biogas inlet pipe (5) all passes through the outside that is positioned at thionizer (3) behind the sidewall of thionizer (3) hermetically, is provided with bleed valve (21) on the elemental sulfur with the intracavity inter-connection of upper thionizer (3) at the sidewall of upper thionizer (3); Bleed valve on the described elemental sulfur (21) is near the bottom of upper thionizer (3);
Nutritive medium fluid infusion case (7) sealing outside with being positioned at lower thionizer (16) of the entrance end of liquid-inlet pipe (8) links to each other, the exit end of liquid-inlet pipe (8) passes through the inner chamber that is arranged in lower thionizer (16) behind the sidewall of lower thionizer (16) hermetically, is provided for controlling the float valve (26) of liquid-inlet pipe (8) conducting at the exit end of liquid-inlet pipe (8); Be provided with the dish type aerator (27) with aeration head (12) in lower thionizer (16), described float valve (26) is positioned at the top of dish type aerator (27); Be positioned at the outside blast pipe (9) of lower thionizer (16) and be connected with aeration head (12) on the dish type aerator (27), at blast pipe (9) intake valve (10) is set; In the bottom of lower thionizer (16) bleed valve (13) under the elemental sulfur with the intracavity inter-connection of lower thionizer (16) is set;
In the upper end of return line (19) lower curved elbow (25) is set, described elbow (25) is connected with the bottom of upper thionizer (3) inner chamber; At return line (19) equilibration tube (22) that the inner chamber make return line (19) is connected with ambient atmosphere is set.
2. Integral biological methane desulfurizer according to claim 1, it is characterized in that: vapor pipe (20) is connected with the first half of lower thionizer (16) inner chamber.
3. Integral biological methane desulfurizer according to claim 2, it is characterized in that: the flow direction of liquid is respectively equipped with strainer (15), recycle pump (17) and variable valve (18) in transfer lime (23) is gone up according to transfer lime (23), the entrance end of described transfer lime (23) and lower thionizer (16) intracavity inter-connection that is positioned at dish type aerator (27) below; In the lower end of strainer (15) bleed valve (14) is set.
4. Integral biological methane desulfurizer according to claim 3 is characterized in that: the upper/lower terminal at described filler (24) respectively arranges the data acquisition unit I (101) that a cover is comprised of temperature sensor and pH value sensor; Be provided for detecting respectively the data acquisition unit II (102) of concentration of hydrogen sulfide and flow in the ingress of biogas inlet pipe (5); Locate to be provided for detecting respectively the gas concentration collector (103) of concentration of hydrogen sulfide and oxygen concentration at methane outlet (1), in the inner chamber of lower thionizer (16), be provided for detecting the data acquisition unit III (104) of fluid temperature, pH value and dissolved oxygen in the lower thionizer (16).
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| JP5330436B2 (en) * | 2011-03-15 | 2013-10-30 | 株式会社東芝 | Biogas biodesulfurization apparatus and cleaning method thereof |
| CN102358857A (en) * | 2011-09-15 | 2012-02-22 | 沈阳航空航天大学 | Biogas desulfurization apparatus of composting reactor |
| CN102604701B (en) * | 2012-03-21 | 2014-03-26 | 山东民和生物科技有限公司 | Methane biodesulfurization method |
| CN102974213B (en) * | 2012-11-28 | 2015-04-22 | 沈阳航空航天大学 | Fully-automatic biogas interior micro-oxygen desulfurization device |
| CN103977703A (en) * | 2014-01-14 | 2014-08-13 | 上海治然环保设备工程有限公司 | Biogas biological desulfurization system |
| CN103980972A (en) * | 2014-06-08 | 2014-08-13 | 山东恒能环保能源设备有限公司 | Biological desulfurization device and process |
| CN106467764A (en) * | 2015-08-20 | 2017-03-01 | 樊军 | A kind of methane bio-desulfurization system |
| CN107557089A (en) * | 2017-10-11 | 2018-01-09 | 南京元凯生物能源环保工程有限公司 | A kind of biological desulfurization process for biogas |
| CN109908717B (en) * | 2019-03-26 | 2021-09-24 | 四川大学 | Biogas/natural gas biological desulfurization method for gas circulation type biological bubble tower |
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