CN103980971A - Methane treatment method and methane treatment system - Google Patents
Methane treatment method and methane treatment system Download PDFInfo
- Publication number
- CN103980971A CN103980971A CN201410234310.XA CN201410234310A CN103980971A CN 103980971 A CN103980971 A CN 103980971A CN 201410234310 A CN201410234310 A CN 201410234310A CN 103980971 A CN103980971 A CN 103980971A
- Authority
- CN
- China
- Prior art keywords
- tower
- gas
- liquid
- decarbonizing tower
- biogas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims description 49
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 100
- 239000007788 liquid Substances 0.000 claims abstract description 89
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 50
- 238000004062 sedimentation Methods 0.000 claims abstract description 28
- 238000005261 decarburization Methods 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims description 111
- 238000006477 desulfuration reaction Methods 0.000 claims description 74
- 239000003345 natural gas Substances 0.000 claims description 30
- 230000023556 desulfurization Effects 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 25
- 230000003009 desulfurizing effect Effects 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 20
- 238000009826 distribution Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 239000004033 plastic Substances 0.000 claims description 11
- 229920003023 plastic Polymers 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 7
- 230000008676 import Effects 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 24
- 239000005864 Sulphur Substances 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 89
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 33
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- 235000011089 carbon dioxide Nutrition 0.000 description 17
- 239000003513 alkali Substances 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 12
- 238000011069 regeneration method Methods 0.000 description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 239000002594 sorbent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 10
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 10
- 239000000428 dust Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000006071 cream Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010669 acid-base reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000003822 preparative gas chromatography Methods 0.000 description 3
- 239000003765 sweetening agent Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 102220043159 rs587780996 Human genes 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 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
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention provides a methane treatment system. The methane treatment system comprises a wet desulphurization tower, a decarburization tower, a dryer, and an inclined plate sedimentation tank, wherein the gas outlet of the wet desulphurization tower is communicated with a gas inlet at the lower part of the decarburization tower, a gas outlet at the upper part of the decarburization tower is communicated with the gas inlet of the dryer, a calcium hydroxide solution inlet is formed at the upper part of the decarburization tower, and a liquid outlet at the lower part of the decarburization tower is communicated with a liquid inlet of the inclined plate sedimentation tank. Compared with the prior art, the system obtains sulphur by virtue of the wet desulphurization tower and obtains calcium carbonate and biogas by virtue of the decarburization tower, so that three valuable resources-sulphur, biogas and calcium carbonate are recycled, and maximum resource utilization of the methane is realized; furthermore, the calcium hydroxide solution is used as an absorption solution of the decarburization tower, the absorption solution is not generated by steam or electrical heating, so that the production cost is lowered, the obtained calcium carbonate can be used by a paper mill for producing, and the resource comprehensive utilization is realized.
Description
Technical field
The invention belongs to resource recovery technical field, relate in particular to a kind of biogas treatment process and marsh gas treating system.
Background technology
Organic waste water in the production process of paper mill can produce biogas after Anaerobic Digestion, and the main component of biogas is methane, carbonic acid gas, a small amount of hydrogen sulfide, moisture and other components.The content of hydrogen sulfide in methane is conventionally at 10000ppm～30000ppm, and meeting heavy corrosion pipeline and equipment etc., and meeting generation sulfurous gas after its burning, cause severe contamination to environment; The content of carbon dioxide in methane is about 35%～40%, can reduce the combustion heat value of biogas, thereby cannot meet the gas quality standard of pipe natural gas and natural gas used for automobile, so in the treating processes of biogas, generally will remove above two kinds of components.
The conventional method of existing desulfurization has three kinds: dry desulfurization, wet desulphurization and biological desulphurization.Wherein, dry desulfurization is to utilize the solid particulate sweetening agents such as ferric oxide, gac, by physical and chemical adsorption effect, remove the hydrogen sulfide in biogas, the sweetening agent loading capacity of this method is little, adsorb after saturated and need to change, and it is larger to change labour intensity, discarded sweetening agent is mishandling simultaneously can cause new pollution again.Therefore, dry desulfurization is more suitable for the biogas essence desulfurization processing that hydrogen sulfide content is low.
Wet desulphurization be take sodium carbonate as alkali source, acid-base reaction while utilizing its aqueous solution to contact with biogas sponges the 2 S component in biogas, utilize under the synergy of a kind of Cobalt Phthalocyanine series catalysts oxygen in air in aqueous sodium carbonate, by the HS in absorption liquid simultaneously
-be oxidized to simple substance S, S is separated as commodity selling from whole desulfurizer, and the solution after sulphur removal is regenerated and is again had the ability of adsorption of hydrogen sulfide, thereby reaches recycle, in actual production process, only need to supplement alkali source and the catalyzer of a small amount of loss.The occasion that wet desulphurization is applicable to is large-minded, hydrogen sulfide content is high, and the larger operating mode of biogas fluctuation of load is also had to good adaptive faculty.
Biological desulphurization is that to take sodium carbonate or sodium hydroxide be alkali source, acid-base reaction while utilizing its aqueous solution to contact with biogas sponges the 2 S component in biogas, then utilize the redox vital movement of microorganism, and in air under the synergy of oxygen, by the HS in absorption liquid
-be oxidized to simple substance S, S is separated as commodity selling from whole desulfurizer, the solution after sulphur removal is regenerated and is again had the ability of adsorption of hydrogen sulfide, recycle, and microorganism experiences growth, breeding, dead life route in this process.Biological desulphurization mainly relies on the normal activities of microorganism and is accomplished, therefore, the stability of operation, control, properties of gas sources and outside atmosphere is had to very harsh requirement, once there is unfavorable factor, the processing efficiency of microorganism just can sharply decline, even bacterial classification mortality and cause device to move.Biological desulphurization, also just in the pilot scale stage, also has a large amount of fundamental researchs and engineering development work to do from engineering application at present.
The conventional method of decarburization comprises: chemical absorption method, PSA method, WATER-WASHING METHOD and membrane separation process.Wherein, chemical absorption method adopts basic solution (alcamines material), utilizes acid-base reaction, absorb the carbonic acid gas in biogas, then by the heating of solution, air lift process, discharge absorbed carbonic acid gas absorption liquid is regenerated, again possess decarburization function.The methane yield of the method can reach more than 99.9%, and methane content can reach more than 99%, and in purified gas, carbon dioxide content is less than 0.1%, but because the regeneration of solution need to be used steam, for the enterprise that there is no steam, this method is limitation slightly, but can solve by setting up steam boiler.
PSA method is to utilize sorbent material different to the adsorptive power of different components, and being adsorbed on loading capacity on sorbent material rises and increases with the dividing potential drop of adsorbate, the characteristic declining with the rising of temperature, realize the separation of different components in biogas, also can realize sorbent material and under high pressure adsorb under low pressure desorption and regeneration simultaneously, make the absorption and regeneration circulation of sorbent material, reach continuous separate from object.This method level of automation is higher, simple to operate, but the specific absorption of methane is low, only have 85%～93%, waste methane resource, and the gas circuit of operational process switches and need to use a large amount of sequencing valves, and one makes easily because dust stops up, cause system fluctuation of service, discarded sorbent material can bring new pollution on the other hand.
WATER-WASHING METHOD is to utilize carbonic acid gas solubleness in water under high normal pressure and temperature or low-pressure low-temperature larger, and the methane less characteristic of solubleness with this understanding, realizes the separated of methane in sewage gas and carbonic acid gas.This method can be removed the 2 S component of part simultaneously, and water source is wide, but after washing, gas product water content increases, and strengthened dehydration load, and plant energy consumption is higher.
Membrane separation process is to utilize the dissolving-rate of diffusion of biogas China different components on polymeric membrane different, realizes decarburization and purifies object.This method can not produce waste liquid and waste solid, relatively environmental protection, but its power consumption is high, and methane yield is very low, and film production technology is still immature, still take at present laboratory and pilot scale research as main.
The processing of existing paper mill to biogas, mainly contains (1) directly combustion method; (2) wet desulphurization recovery sulphur, and biogas after desulfurization is as boiler oil; (3) first adopt wet desulphurization, then adopt chemical absorption method or PSA method or WATER-WASHING METHOD carbon dioxide removal, the biogas after desulfuration carbon elimination is incorporated to urban pipe network or as natural gas used for automobile through aftertreatment.But aforesaid method all can not be recycled carbonic acid gas.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of biogas treatment process and marsh gas treating system, this treatment process recoverable carbonic acid gas.
The invention provides a kind of biogas treatment process, comprising:
Biogas is carried out, after wet desulphurization processing, obtaining the gas after desulfurization;
Gas after described desulfurization is mixed with aqua calcis, carry out carbonization treatment, obtain gas and suspension after decarburization;
After gas after described decarburization is dried, obtain bio-natural gas;
Described suspension is staticly settled, obtain calcium carbonate.
Preferably, described carbonization treatment adopts decarbonizing tower to carry out; The mass transfer section of described decarbonizing tower is divided into three layers; Lower floor and middle layer all adopt anti-stop-type spiral nozzle to carry out aqua calcis distribution; Upper strata adopts plastic filler.
Preferably, the concentration of described aqua calcis is 1.4～1.7g/L; The pH value of described aqua calcis is 9.0～12.5.
The present invention also provides a kind of marsh gas treating system, comprising: wet desulfuration tower (3), decarbonizing tower (15), moisture eliminator (17), inclined-plate clarifying basin (20);
The pneumatic outlet of described wet desulfuration tower (3) is connected with the gas inlet of described decarbonizing tower (15) bottom;
The pneumatic outlet on described decarbonizing tower (15) top is connected with the gas inlet of described moisture eliminator (17);
The top of described decarbonizing tower (15) has aqua calcis import;
The liquid exit of described decarbonizing tower (15) bottom is connected with the liquid inlet of described inclined-plate clarifying basin (20).
Preferably, the mass transfer section of described decarbonizing tower (15) is divided into three layers; Lower floor and middle layer all adopt anti-stop-type spiral nozzle to carry out aqua calcis distribution; Upper strata adopts plastic filler.
Preferably, described plastic filler is Pall ring or rectangular saddle ring.
Preferably, the pneumatic outlet of described wet desulfuration tower (3) is connected with the gas inlet of described decarbonizing tower (15) bottom by dry-type desulfurizing tower (5).
Preferably, the liquid exit of described wet desulfuration tower (3) is connected with the liquid-inlet of solution regenerator (6); Described solution regenerator (6) has air intlet.
Preferably, the pneumatic outlet of described wet desulfuration tower (3) is connected with the gas inlet of described decarbonizing tower (15) bottom by gas compressor (14).
Preferably, the liquid exit of described decarbonizing tower (15) bottom is connected with the liquid inlet of described inclined-plate clarifying basin by preliminary sedimentation tank (19).
The invention provides a kind of marsh gas treating system, comprising: wet desulfuration tower (3), decarbonizing tower (15), moisture eliminator (17), inclined-plate clarifying basin (20); The pneumatic outlet of described wet desulfuration tower (3) is connected with the gas inlet of described decarbonizing tower (15) bottom; The pneumatic outlet on described decarbonizing tower (15) top is connected with the gas inlet of described moisture eliminator (17); The top of described decarbonizing tower (15) has aqua calcis import; The liquid exit of described decarbonizing tower (15) bottom is connected with the liquid inlet of described inclined-plate clarifying basin (20).Compared with prior art, the present invention obtains sulphur by wet desulfuration tower, decarbonizing tower obtains calcium carbonate, has realized the recovery of sulphur, bio-natural gas, three kinds of valuable resources of calcium carbonate, has reached the utilization of biogas maximum resource, simultaneously, adopt aqua calcis as the absorption liquid of decarbonizing tower, and absorption liquid is without steam or electrically heated regeneration, has reduced production cost, the calcium carbonate obtaining can be used for the production in paper mill itself, has realized the comprehensive utilization of resource.
Accompanying drawing explanation
Fig. 1 is desulphurization system schematic diagram of the present invention;
Fig. 2 is decarburization of the present invention and reclaims calcium carbonate system schematic;
Fig. 3 is marsh gas treating system overall process schematic diagram provided by the invention.
Embodiment
Refer to Fig. 1 and Fig. 2, Fig. 1 is desulphurization system schematic diagram, and wherein 1 is pre-separator, 2 is gas blower, and 3 is wet desulfuration tower, and 4 is the first gas-liquid separator, 5 is dry-type desulfurizing tower, 6 is solution regenerator, and 7 is the distribution orifice of solution regenerator inside, and 8 is air-dry groove, 9 is surge tank, 10 is desulfur pump, and 11 is liquid pool, and 12 is dosing pump; Fig. 2 is decarburization and recovery calcium carbonate system schematic, and wherein 13 is dust removal filter, and 14 is gas compressor, and 15 is decarbonizing tower, 16 is the second gas-liquid separator, and 17 is moisture eliminator, and 18 is Liquid level adjusting valve, and 19 is preliminary sedimentation tank, 20 is inclined-plate clarifying basin, and 21 is slush pump, and 22 is equalizing tank, and 23 is pump.
The invention provides a kind of marsh gas treating system, comprising: wet desulfuration tower (3), decarbonizing tower (15), moisture eliminator (17), inclined-plate clarifying basin (20); The pneumatic outlet of described wet desulfuration tower (3) is connected with the gas inlet of described decarbonizing tower (15) bottom; The pneumatic outlet on described decarbonizing tower (15) top is connected with the gas inlet of described moisture eliminator (17); The top of described decarbonizing tower (15) has aqua calcis import; The liquid exit of described decarbonizing tower (15) bottom is connected with the liquid inlet of described inclined-plate clarifying basin (20).
According to the present invention, described wet desulfuration tower (3) is for the wet desulphurization of biogas, described biogas is biogas well known to those skilled in the art, there is no special restriction, is preferably the biogas that the organic waste water in the production process of paper mill produces after Anaerobic Digestion in the present invention.In biogas, contain moisture, therefore, the present invention preferably also comprises pre-separator (1); The pneumatic outlet of described pre-separator (1) is connected with the gas feed of described wet desulfuration tower (3).Pre-separator is for separating of the moisture going out in biogas.
Biogas is after pre-separator (1) dehydration, preferably enter in gas blower (2), after gas blower pressurization, enter in wet desulfuration tower (3), the pneumatic outlet of described pre-separator (1) is preferably connected with the gas feed of described wet desulfuration tower (3) by gas blower (2).Gas blower, for pressurizeing to entering the gas of wet desulfuration tower (3), is preferably forced into 15～30kPa.
The gas feed of wet desulfuration tower (3) is positioned at bottom, the biogas after pressurization enters from the bottom of wet desulfuration tower (3), doctor solution counter current contact from below to up with spraying from tower top, hydrogen sulfide is absorbed and proceeds to doctor solution, thereby the content of the hydrogen sulfide in methane after purification is removed to below 50ppm; In described doctor solution, containing the blue or green cobalt of alkali source and titanium is oxygen carrier catalyzer; Described alkali source is alkali source well known to those skilled in the art, there is no special restriction, is preferably sodium carbonate.
The liquid exit of wet desulfuration tower in the present invention (3) is preferably connected with the liquid-inlet of solution regenerator (6); Described solution regenerator (6) has air intlet.Doctor solution after purification enters in solution regenerator through liquid exit, and the doctor solution after preferably purifying stops after 15～20min in the bottom of wet desulfuration tower, then enters in solution regenerator.The liquid-inlet of described solution regenerator is positioned at bottom, and liquid distributor is preferably contained in the inside of solution regenerator, doctor solution after purification is uniformly distributed by liquid distributor, pressurized air enters through the air intlet of solution regenerator (6), gas distributor in solution regenerator distributes, mix with the doctor solution after purifying, gas-liquid mixture is upwards operation together after the inner distribution orifice (7) of solution regenerator (6) is uniform more again, and the blue or green cobalt of titanium in the doctor solution after purification is that oxygen carrier catalyzer is by HS in solution
-be oxidized to simple substance S, by receiving airborne oxygen again to become oxygen carrier catalyzer, realize regeneration simultaneously.
The top of described solution regenerator (6) is preferably connected with air-dry groove (8); The liquid exit of described solution regenerator (6) is preferably connected with desulfur pump (10) by surge tank (9); The liquid exit of described air-dry groove (8) is preferably connected with desulfur pump (10) by surge tank (9).Elemental sulfur is had the entrained absorption of air bubble of huge surface area and is enriched in the top of solution regenerator (6), and enter air-dry groove (8) by overflow, filter excess is sulphur cream, can be used as commodity selling, and the filtrate system of sending back to participates in process of wet desulphurization again.Doctor solution after regeneration desulfuration possesses absorptive function again, and doctor solution and filtrate flow in surge tank (9), and sends into wet desulfuration tower (3) top through desulfur pump (10), recycles.
For fear of long-time reaction, cause the consumption of alkali source and catalyzer in doctor solution to reduce and affect purification rate and effect, the present invention preferably also comprises liquid pool (11), and the liquid exit of described liquid pool (11) is connected with surge tank (9) by dosing pump (12).The a small amount of alkali source consuming in scavenging process and catalyzer are adjusted in liquid pool (11), and supplement and enter in desulphurization system through dosing pump (12).
In order to reduce moisture and sulphur atom content in the biogas after purification, the pneumatic outlet of described wet desulfuration tower (3) is preferably connected with the gas inlet of dry-type desulfurizing tower (5).In dry-type desulfurizing tower (5), by ferric oxide bed, further hydrogen sulfide content is down to below 1ppm.
In order to strengthen the effect of dry type desulfurizing and to reduce the moisture in the biogas after purifying, the pneumatic outlet of described wet desulfuration tower (3) is preferably connected with the gas inlet of dry-type desulfurizing tower (5) by the first gas-liquid separator (4).Separable by the first gas-liquid separator (4) and recovery is carried secretly a small amount of doctor solution.
According to the present invention, the pneumatic outlet of described dry-type desulfurizing tower (5) is preferably connected with the gas inlet of described decarbonizing tower (15) bottom by gas compressor (14).Wherein, in order to reduce the dust impurity in gas after desulfurization, the pneumatic outlet of preferred dry thionizer (5) is connected with gas compressor (14) by dust removal filter (13).Gas after desulfurization, through gas compressor supercharging, after being preferably pressurized to 0.6～1.0MPa, enters decarbonizing tower (15).
The top of decarbonizing tower (15) has aqua calcis import, gas after desulfurization in decarbonizing tower (15) from below to up with from tower top spray and aqua calcis counter current contact, carbonic acid gas in gas by solution, absorbed and and methane separation, CO
2+ Ca (OH)
2=CaCO
3+ H
2o; By the methane of enrichment, being become bio-natural gas discharges from decarbonizing tower top.
For avoiding the calcium carbonate powders that carbonic acid gas and calcium hydroxide reaction produce to stop up decarbonizing tower, the mass transfer section of decarbonizing tower described in the present invention (15) is preferably three layers: lower floor, middle layer and upper strata; Lower floor and middle layer all adopt anti-stop-type spiral nozzle to carry out aqua calcis distribution; Upper strata adopts plastic filler.Decarbonizing tower (15) bottom and middle carbon dioxide in gas concentration are higher, the concentration of product calcium carbonate is also higher, the distribution that adopts anti-clogging plug spiral nozzle to carry out aqua calcis can solve the blockage problem of equipment well, also can play good assimilation effect simultaneously.Upper strata adopts the plastic filler of large specification, is preferably Pall ring or rectangular saddle ring.Utilize specific surface area that filler is larger and mass transfer liquid level renewal speed faster, can realize the carbonic acid gas of trace in gas is carried out to the de-processing of essence, in the bio-natural gas that makes finally to obtain, methane content and carbon dioxide content meet < < compressed natural gas used as vehicle fuel > > gas quality standard, also have anti-stifled effect preferably simultaneously.
From decarbonizing tower (15) top bio-natural gas out, because humidity is larger, cannot reach the dew point requirement of civilian or industrial natural gas, need through further dry.The pneumatic outlet on described decarbonizing tower (15) top is connected with the gas inlet of described moisture eliminator (17).In described moisture eliminator (17), preferably comprise one or both in molecular sieve, silica gel and alumina adsorbant, utilize Temp .-changing adsorption principle, realize the dry of bio-natural gas, make its dew point reach-45 ℃, and can be by the adjustment of Controlling System, realize the adjusting of dew point, dried bio-natural gas is sent to subsequent handling and can be incorporated to urban pipe network or prepares compressed natural gas used as vehicle fuel.
The present invention preferably also comprises the second gas-liquid separator (16); The pneumatic outlet on described decarbonizing tower (15) top is connected with the gas inlet of described moisture eliminator (17) by the second gas-liquid separator (16).By the recyclable a small amount of aqua calcis carried under one's arms of the second gas-liquid separator (16), reduce the moisture that enters gas in moisture eliminator (17), and then reduce the load of moisture eliminator (17).
The liquid exit of described decarbonizing tower (15) bottom is connected with the liquid inlet of described inclined-plate clarifying basin (20).With solution, the liquid exit by decarbonizing tower (15) bottom enters inclined-plate clarifying basin (20) to the calcium carbonate components producing in decarbonizing tower (15), and described decarbonizing tower (15) liquid exit goes out preferably also to comprise that Liquid level adjusting valve (18) is for the flow of regulator solution.
According to invention, the liquid exit of described decarbonizing tower (15) bottom is preferably connected with the liquid inlet of described inclined-plate clarifying basin (20) by preliminary sedimentation tank (19).Preliminary sedimentation tank (19) plays the shock absorption to solution, also can realize the primary sedimentation of calcium carbonate simultaneously; The time stopping in preliminary sedimentation tank (19) is preferably 40～60min.The solution that contains a small amount of calcium carbonate granule thing overflowing from preliminary sedimentation tank top flows into inclined-plate clarifying basin (20), further tiny calcium carbonate granule trapping is precipitated; The residence time of solution in inclined-plate clarifying basin (20) is preferably 30～40min.Described preliminary sedimentation tank (19) all preferably adopts the design of bucket type with the bottom of described inclined-plate clarifying basin (20), is beneficial to sedimentary gathering.Because desulfurization stage is clean by hydrogen sulfide treatment, therefore, the purity of decarbonization process by product calcium carbonate is higher.
Preliminary sedimentation tank (19) is all preferably connected with slush pump (21) with bottom in inclined-plate clarifying basin (20).Bottom precipitation can regularly be released and is sent to finishing department by slush pump (21), is prepared into the pearl filler that meets paper machine room production use.
The liquid exit of described inclined-plate clarifying basin (20) is preferably connected with equalizing tank (22).The supernatant liquid flowing out in inclined-plate clarifying basin (20) flows in equalizing tank (22), passes through hydrogen make-up calcium oxide and regulates after pH value, by being pumped into the new absorption cleaning circulation of beginning in decarbonizing tower (15) in equalizing tank (22).
Fig. 3 is marsh gas treating system overall process schematic diagram provided by the invention; The present invention obtains sulphur by wet desulfuration tower, decarbonizing tower obtains calcium carbonate, realized the backflow of sulphur, bio-natural gas, calcium carbonate three kinds of valuable resources, reach the utilization of biogas maximum resource, meanwhile, adopted aqua calcis as the absorption liquid of decarbonizing tower, and absorption liquid is without steam or electrically heated regeneration, reduced production cost, the calcium carbonate obtaining can be used for the production in paper mill itself, has realized the comprehensive utilization of resource.
The present invention also provides a kind of method that above-mentioned marsh gas treating system is processed biogas of applying, and comprising: biogas is carried out, after wet desulphurization processing, obtaining the gas after desulfurization; Gas after described desulfurization is mixed with aqua calcis, carry out carbonization treatment, obtain gas and suspension after decarburization; After gas after described decarburization is dried, obtain bio-natural gas; Described suspension is staticly settled, obtain calcium carbonate.
Wherein, described biogas is same as above, does not repeat them here.
Described biogas preferably, first through except water treatment, is isolated after liquid water, then is carried out wet desulphurization processing.After processing, can reduce the content of moisture in biogas.The method that the method that described wet desulphurization is processed is wet desulphurization well known to those skilled in the art, there is no special restriction, and the present invention preferably adopts that to contain alkali source and titanium green grass or young crops cobalt be that the solution of oxygen carrier catalyzer is doctor solution; Described alkali source is alkali source well known to those skilled in the art, there is no special restriction, is preferably sodium carbonate; In doctor solution, the concentration of alkali source is preferably 3～7g/L, and total alkalinity is preferably 0.3～0.6N; The pH value of described doctor solution is preferably 8.5～9.0.The blue or green cobalt of titanium in doctor solution after purification is that oxygen carrier catalyzer is by HS in solution
-be oxidized to simple substance S, realize regeneration simultaneously by receiving airborne oxygen again to become oxygen carrier catalyzer, the doctor solution after regeneration desulfuration possesses absorptive function again, can repeat to use as the doctor solution of wet desulphurization.
In order to reduce moisture and the sulphur atom content in the biogas after purification, the gas after wet desulphurization is processed preferably carries out dry type desulfurizing processing again, by ferric oxide bed, further hydrogen sulfide content is down to below 1ppm, obtains the gas after desulfurization.
The effect of processing in order to strengthen dry type desulfurizing, and reduce the moisture in the gas after desulfurization, the gas after wet desulphurization is processed is preferably first through except water treatment, then carries out dry type desulfurizing processing.
Gas after described desulfurization preferably after dust removal process, then mixes with aqua calcis, carries out carbonization treatment, obtains gas and suspension after carbonization treatment.Wherein, the concentration of described aqua calcis is preferably 1.4～1.7g/L; The pH value of described aqua calcis is preferably 9.0～12.5.
Described carbonization treatment preferably adopts decarbonizing tower to carry out, and described decarbonizing tower is same as above, does not repeat them here.
Carbonic acid gas in gas after desulfurization and calcium hydroxide reaction, generate calcium carbonate; Described suspension is staticly settled, obtain calcium carbonate.The described method staticly settling is method well known to those skilled in the art, there is no special restriction, preferably adopts secondary sedimentation in the present invention, and the time of precipitation is preferably 40～60min for the first time, and the time of precipitation is preferably 30～40min for the second time.
According to the present invention, after the gas after described decarburization is dried, obtain bio-natural gas.Wherein, described dry method is method well known to those skilled in the art, there is no special restriction, and the present invention preferably adopts sorbent material to be dried; Described sorbent material is sorbent material well known to those skilled in the art, there is no special restriction, the present invention preferably adopts one or both in molecular sieve, silica gel and alumina adsorbant, utilizes Temp .-changing adsorption principle, realize the dry of bio-natural gas, make its dew point reach-45 ℃.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of biogas treatment process provided by the invention and marsh gas treating system are described in detail.
In following examples, reagent used is commercially available.
Embodiment 1
1.1 provide the marsh gas treating system shown in Fig. 1 and Fig. 2: wet desulfuration tower (3), decarbonizing tower (15), moisture eliminator (17), inclined-plate clarifying basin (20); The pneumatic outlet of pre-separator (1) is connected with the gas feed of wet desulfuration tower (3) by gas blower (2); The pneumatic outlet of wet desulfuration tower (3) is connected with dry-type desulfurizing tower (5) by the first gas-liquid separator (4); The liquid exit of wet desulfuration tower (3) is connected with the liquid-inlet of solution regenerator (6); Described solution regenerator (6) has air intlet; The liquid exit of solution regenerator (6) is connected with air-dry groove (8); Dry-type desulfurizing tower (5) is connected with the gas inlet of decarbonizing tower (15) with gas compressor (14) by dust removal filter (13) successively; The pneumatic outlet of decarbonizing tower (15) is connected with moisture eliminator (17) by the second gas-liquid separator (16); The liquid exit of decarbonizing tower (15) is connected with preliminary sedimentation tank (19) by Liquid level adjusting valve (18); The liquid exit of preliminary sedimentation tank (19) is connected with inclined-plate clarifying basin (20); Preliminary sedimentation tank (19) is connected with slush pump (21) respectively with the bottom of inclined-plate clarifying basin (20).Wherein, the mass transfer section of decarbonizing tower (15) is divided into three layers: lower floor, middle layer and upper strata; Lower floor and middle layer adopt anti-stop-type spiral nozzle to carry out the distribution of aqua calcis; Upper strata adopts Pall ring to carry out filler.
1.2 desulfurization: wet desulphurization+fine desulfurization process by dry, from anaerobic digestor or the next normal pressure biogas of gas holder, through pre-separator (1), isolating after liquid water, enter gas blower (2) and be increased to the bottom that then 20kPa enters wet desulfuration tower (2), (it is oxygen carrier catalyzer that aqueous sodium carbonate contains Cobalt Phthalocyanine to doctor solution from below to up with spraying from tower top, the pH value of doctor solution is 8.5) counter current contact, hydrogen sulfide is absorbed and proceeds to doctor solution, in purified gas, hydrogen sulfide content is removed to below 50ppm, purified gas enters in the first gas-liquid separator (4), separated and recovery is carried under one's arms a small amount of doctor solution, entering dry-type desulfurizing tower (5), by ferric oxide bed, further hydrogen sulfide content is down to below 1ppm, and pass into afterwards in gas compressor (14) through dust removal filter (13),
The doctor solution that has absorbed hydrogen sulfide stops after 18min in wet desulfuration tower (3) bottom, pass into solution regenerator (6) bottom, and be uniformly distributed by liquid distributor, in the bottom of solution regenerator (6), by gas distributor, pass into pressurized air simultaneously, gas-liquid mixture upwards operation together after distribution orifice (7) is uniform more again, the Cobalt Phthalocyanine in doctor solution is that oxygen carrier catalyzer is by the HS in solution
-be oxidized to simple substance S, by receiving airborne oxygen again to become oxygen carrier catalyzer, realize regeneration simultaneously, simple substance S there is the entrained absorption of air bubble of huge surface area and negative pole in solution regenerator (6) top, and enter air-dry groove (8) by overflow, filter excess is sulphur cream, can be used as commodity selling; And filtrate flows in liquid pool (11), then pass in surge tank (9) through dosing pump (12), and send into wet desulfuration tower (3) tower top through desulfur pump (10), recycle.The a small amount of sodium carbonate consuming in sweetening process and Cobalt Phthalocyanine are that oxygen carrier catalyzer is adjusted in liquid pool (11).
1.3 decarburizations: the purified gas after desulfurization is pressurized to after 0.8MPa by gas compressor (14), pass into the bottom of decarbonizing tower (15), aqua calcis (the pH value of aqua calcis is 9.5) counter current contact from below to up with spraying from tower top, upper strata filler is that 5m is high, diameter is the plastics Pall ring filler of 100mm, carbonic acid gas in gas by solution, absorb to be generated calcium carbonate and and methane separation, by the methane of enrichment, being become bio-natural gas discharges from the top of decarbonizing tower (15), through the second gas-liquid separator (16), pass in moisture eliminator (17), in moisture eliminator (17), comprise molecular sieve and silica gel as sorbent material, utilize Temp .-changing adsorption principle, the dew point of bio-natural gas is reached-45 ℃.
1.4 calcium carbonate are settlement separate: with solution, the Liquid level adjusting valve (18) by decarbonizing tower (15) bottom enters in preliminary sedimentation tank (19) calcium carbonate components, stop 50min, realize the primary sedimentation of calcium carbonate, the solution that contains a small amount of calcium carbonate granule thing overflowing from preliminary sedimentation tank (19) top flows into inclined-plate clarifying basin (20), stop 35min, further tiny calcium carbonate granule trapping is settled down.Preliminary sedimentation tank (19) all adopts the design of bucket type with the bottom of inclined-plate clarifying basin (20), adopts slush pump (21) regularly the calcium carbonate under precipitation to be released and is sent to finishing department, is prepared into the pearl filler that meets paper machine room production use.
The upper strata liquid flowing out from inclined-plate clarifying basin (20) flows into equalizing tank (22), after hydrogen make-up calcium oxide and adjusting pH value to 9.5, is sent into the top of decarbonizing tower (15) by pump (23), and decarburization circulates.
Purified gas according to GB/T11060.1-1998 after to wet desulphurization in 1.2 and the hydrogen sulfide content in the purified gas after dry type desulfurizing are measured, after iodometric determination, the hydrogen sulfide content obtaining in the purified gas after result wet desulphurization is 45ppm, and the content of the hydrogen sulfide in the purified gas after dry type desulfurizing is 0.1ppm.
According to GB/T2449-2006 industrial sulphur, the sulphur cream obtaining in 1.2 is measured, obtaining wherein sulphur content is 80%.
According to the compositional analysis of GB/T13610-1992 Sweet natural gas, adopt vapor-phase chromatography to analyze the bio-natural gas obtaining in 1.3, obtaining the wherein content of methane is 97%, the content of carbonic acid gas is 2.5%.
According to HG/T3249.1-2008 paper industry, with water-ground limestone, the calcium carbonate obtaining in 1.4 is analyzed, obtained wherein calcium carbonate content and be greater than 98.8%.
Embodiment 2
2.1 marsh gas treating systems that adopt embodiment 1 to provide.
2.2 desulfurization: wet desulphurization+fine desulfurization process by dry, from anaerobic digestor or the next normal pressure biogas of gas holder, through pre-separator (1), isolating after liquid water, enter gas blower (2) and be increased to the bottom that then 20kPa enters wet desulfuration tower (2), (it is oxygen carrier catalyzer that aqueous sodium carbonate contains Cobalt Phthalocyanine to doctor solution from below to up with spraying from tower top, the pH value of doctor solution is 8.5) counter current contact, hydrogen sulfide is absorbed and proceeds to doctor solution, in purified gas, hydrogen sulfide content is removed to below 50ppm, purified gas enters in the first gas-liquid separator (4), separated and recovery is carried under one's arms a small amount of doctor solution, entering dry-type desulfurizing tower (5), by ferric oxide bed, further hydrogen sulfide content is down to below 1ppm, and pass into afterwards in gas compressor (14) through dust removal filter (13),
The doctor solution that has absorbed hydrogen sulfide stops after 18min in wet desulfuration tower (3) bottom, pass into solution regenerator (6) bottom, and be uniformly distributed by liquid distributor, in the bottom of solution regenerator (6), by gas distributor, pass into pressurized air simultaneously, gas-liquid mixture upwards operation together after distribution orifice (7) is uniform more again, the Cobalt Phthalocyanine in doctor solution is that oxygen carrier catalyzer is by the HS in solution
-be oxidized to simple substance S, by receiving airborne oxygen again to become oxygen carrier catalyzer, realize regeneration simultaneously, simple substance S there is the entrained absorption of air bubble of huge surface area and negative pole in solution regenerator (6) top, and enter air-dry groove (8) by overflow, filter excess is sulphur cream, can be used as commodity selling; And filtrate flows in liquid pool (11), then pass in surge tank (9) through dosing pump (12), and send into wet desulfuration tower (3) tower top through desulfur pump (10), recycle.The a small amount of sodium carbonate consuming in sweetening process and Cobalt Phthalocyanine are that oxygen carrier catalyzer is adjusted in liquid pool (11).
2.3 decarburizations: the purified gas after desulfurization is pressurized to after 1.2MPa by gas compressor (14), pass into the bottom of decarbonizing tower (15), aqua calcis (the pH value of aqua calcis is 9.5) counter current contact from below to up with spraying from tower top, upper strata filler is that 5m is high, diameter is the plastics Pall ring filler of 100mm, carbonic acid gas in gas by solution, absorb to be generated calcium carbonate and and methane separation, by the methane of enrichment, being become bio-natural gas discharges from the top of decarbonizing tower (15), through the second gas-liquid separator (16), pass in moisture eliminator (17), in moisture eliminator (17), comprise molecular sieve and silica gel as sorbent material, utilize Temp .-changing adsorption principle, the dew point of bio-natural gas is reached-45 ℃.
2.4 calcium carbonate are settlement separate: with solution, the Liquid level adjusting valve (18) by decarbonizing tower (15) bottom enters in preliminary sedimentation tank (19) calcium carbonate components, stop 50min, realize the primary sedimentation of calcium carbonate, the solution that contains a small amount of calcium carbonate granule thing overflowing from preliminary sedimentation tank (19) top flows into inclined-plate clarifying basin (20), stop 35min, further tiny calcium carbonate granule trapping is settled down.Preliminary sedimentation tank (19) all adopts the design of bucket type with the bottom of inclined-plate clarifying basin (20), adopts slush pump (21) regularly the calcium carbonate under precipitation to be released and is sent to finishing department, is prepared into the pearl filler that meets paper machine room production use.
The upper strata liquid flowing out from inclined-plate clarifying basin (20) flows into equalizing tank (22), after hydrogen make-up calcium oxide and adjusting pH value to 9.5, is sent into the top of decarbonizing tower (15) by pump (23), and decarburization circulates.
Purified gas according to GB/T11060.1-1998 after to wet desulphurization in 2.2 and the hydrogen sulfide content in the purified gas after dry type desulfurizing are measured, after iodometric determination, the hydrogen sulfide content obtaining in the purified gas after result wet desulphurization is 45ppm, and the content of the hydrogen sulfide in the purified gas after dry type desulfurizing is 0.1ppm.
According to GB/T2449-2006 industrial sulphur, the sulphur cream obtaining in 1.2 is measured, obtaining wherein sulphur content is 80%.
According to the compositional analysis of GB/T13610-1992 Sweet natural gas, adopt vapor-phase chromatography to analyze the bio-natural gas obtaining in 1.3, obtaining the wherein content of methane is 97.5%, the content of carbonic acid gas is 2.1%.
According to HG/T3249.1-2008 paper industry, with water-ground limestone, the calcium carbonate obtaining in 2.4 is analyzed, obtained wherein calcium carbonate content and be greater than 98.8%, D50=2.5 μ m.
Embodiment 3
3.1 the marsh gas treating system providing in embodiment 1 is provided.
3.2 desulfurization: wet desulphurization+fine desulfurization process by dry, from anaerobic digestor or the next normal pressure biogas of gas holder, through pre-separator (1), isolating after liquid water, enter gas blower (2) and be increased to the bottom that then 20kPa enters wet desulfuration tower (2), (it is oxygen carrier catalyzer that aqueous sodium carbonate contains Cobalt Phthalocyanine to doctor solution from below to up with spraying from tower top, the pH value of doctor solution is 8.5) counter current contact, hydrogen sulfide is absorbed and proceeds to doctor solution, in purified gas, hydrogen sulfide content is removed to below 50ppm, purified gas enters in the first gas-liquid separator (4), separated and recovery is carried under one's arms a small amount of doctor solution, entering dry-type desulfurizing tower (5), by ferric oxide bed, further hydrogen sulfide content is down to below 1ppm, and pass into afterwards in gas compressor (14) through dust removal filter (13),
The doctor solution that has absorbed hydrogen sulfide stops after 18min in wet desulfuration tower (3) bottom, pass into solution regenerator (6) bottom, and be uniformly distributed by liquid distributor, in the bottom of solution regenerator (6), by gas distributor, pass into pressurized air simultaneously, gas-liquid mixture upwards operation together after distribution orifice (7) is uniform more again, the Cobalt Phthalocyanine in doctor solution is that oxygen carrier catalyzer is by the HS in solution
-be oxidized to simple substance S, by receiving airborne oxygen again to become oxygen carrier catalyzer, realize regeneration simultaneously, simple substance S there is the entrained absorption of air bubble of huge surface area and negative pole in solution regenerator (6) top, and enter air-dry groove (8) by overflow, filter excess is sulphur cream, can be used as commodity selling; And filtrate flows in liquid pool (11), then pass in surge tank (9) through dosing pump (12), and send into wet desulfuration tower (3) tower top through desulfur pump (10), recycle.The a small amount of sodium carbonate consuming in sweetening process and Cobalt Phthalocyanine are that oxygen carrier catalyzer is adjusted in liquid pool (11).
3.3 decarburizations: the purified gas after desulfurization is pressurized to after 1.2MPa by gas compressor (14), pass into the bottom of decarbonizing tower (15), aqua calcis (the pH value of aqua calcis is 12) counter current contact from below to up with spraying from tower top, upper strata filler is that 5m is high, diameter is the plastics Pall ring filler of 100mm, carbonic acid gas in gas by solution, absorb to be generated calcium carbonate and and methane separation, by the methane of enrichment, being become bio-natural gas discharges from the top of decarbonizing tower (15), through the second gas-liquid separator (16), pass in moisture eliminator (17), in moisture eliminator (17), comprise molecular sieve and silica gel as sorbent material, utilize Temp .-changing adsorption principle, the dew point of bio-natural gas is reached-45 ℃.
3.4 calcium carbonate are settlement separate: with solution, the Liquid level adjusting valve (18) by decarbonizing tower (15) bottom enters in preliminary sedimentation tank (19) calcium carbonate components, stop 50min, realize the primary sedimentation of calcium carbonate, the solution that contains a small amount of calcium carbonate granule thing overflowing from preliminary sedimentation tank (19) top flows into inclined-plate clarifying basin (20), stop 35min, further tiny calcium carbonate granule trapping is settled down.Preliminary sedimentation tank (19) all adopts the design of bucket type with the bottom of inclined-plate clarifying basin (20), adopts slush pump (21) regularly the calcium carbonate under precipitation to be released and is sent to finishing department, is prepared into the pearl filler that meets paper machine room production use.
The upper strata liquid flowing out from inclined-plate clarifying basin (20) flows into equalizing tank (22), after hydrogen make-up calcium oxide and adjusting pH value to 12, is sent into the top of decarbonizing tower (15) by pump (23), and decarburization circulates.
Purified gas according to GB/T11060.1-1998 after to wet desulphurization in 3.2 and the hydrogen sulfide content in the purified gas after dry type desulfurizing are measured, after iodometric determination, the hydrogen sulfide content obtaining in the purified gas after result wet desulphurization is 45ppm, and the content of the hydrogen sulfide in the purified gas after dry type desulfurizing is 0.1ppm.
According to GB/T2449-2006 industrial sulphur, the sulphur cream obtaining in 3.2 is measured, obtaining wherein sulphur content is 80%.
According to the compositional analysis of GB/T13610-1992 Sweet natural gas, adopt vapor-phase chromatography to analyze the bio-natural gas obtaining in 3.3, obtaining the wherein content of methane is 98%, the content of carbonic acid gas is 1.3%.
According to HG/T3249.1-2008 paper industry, with water-ground limestone, the calcium carbonate obtaining in 3.4 is analyzed, obtained wherein calcium carbonate content and be greater than 98.8%, D50=2.5 μ m.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a biogas treatment process, is characterized in that, comprising:
Biogas is carried out, after wet desulphurization processing, obtaining the gas after desulfurization;
Gas after described desulfurization is mixed with aqua calcis, carry out carbonization treatment, obtain gas and suspension after decarburization;
After gas after described decarburization is dried, obtain bio-natural gas;
Described suspension is staticly settled, obtain calcium carbonate.
2. biogas treatment process according to claim 1, is characterized in that, described carbonization treatment adopts decarbonizing tower to carry out; The mass transfer section of described decarbonizing tower is divided into three layers; Lower floor and middle layer all adopt anti-stop-type spiral nozzle to carry out aqua calcis distribution; Upper strata adopts plastic filler.
3. biogas treatment process according to claim 1, is characterized in that, the concentration of described aqua calcis is 0.1～1.7g/L; The pH value of described aqua calcis is 9.0～12.5.
4. a marsh gas treating system, is characterized in that, comprising: wet desulfuration tower (3), decarbonizing tower (15), moisture eliminator (17), inclined-plate clarifying basin (20);
The pneumatic outlet of described wet desulfuration tower (3) is connected with the gas inlet of described decarbonizing tower (15) bottom;
The pneumatic outlet on described decarbonizing tower (15) top is connected with the gas inlet of described moisture eliminator (17);
The top of described decarbonizing tower (15) has aqua calcis import;
The liquid exit of described decarbonizing tower (15) bottom is connected with the liquid inlet of described inclined-plate clarifying basin (20).
5. marsh gas treating system according to claim 4, is characterized in that, the mass transfer section of described decarbonizing tower (15) is divided into three layers; Lower floor and middle layer all adopt anti-stop-type spiral nozzle to carry out aqua calcis distribution; Upper strata adopts plastic filler.
6. marsh gas treating system according to claim 4, is characterized in that, described plastic filler is Pall ring or rectangular saddle ring.
7. marsh gas treating system according to claim 4, is characterized in that, the pneumatic outlet of described wet desulfuration tower (3) is connected with the gas inlet of described decarbonizing tower (15) bottom by dry-type desulfurizing tower (5).
8. marsh gas treating system according to claim 4, is characterized in that, the liquid exit of described wet desulfuration tower (3) is connected with the liquid-inlet of solution regenerator (6); Described solution regenerator (6) has air intlet.
9. marsh gas treating system according to claim 4, is characterized in that, the pneumatic outlet of described wet desulfuration tower (3) is connected with the gas inlet of described decarbonizing tower (15) bottom by gas compressor (14).
10. marsh gas treating system according to claim 4, is characterized in that, the liquid exit of described decarbonizing tower (15) bottom is connected with the liquid inlet of described inclined-plate clarifying basin by preliminary sedimentation tank (19).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410234310.XA CN103980971A (en) | 2014-05-29 | 2014-05-29 | Methane treatment method and methane treatment system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410234310.XA CN103980971A (en) | 2014-05-29 | 2014-05-29 | Methane treatment method and methane treatment system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103980971A true CN103980971A (en) | 2014-08-13 |
Family
ID=51273143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410234310.XA Pending CN103980971A (en) | 2014-05-29 | 2014-05-29 | Methane treatment method and methane treatment system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103980971A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479777A (en) * | 2014-11-20 | 2015-04-01 | 中国石油大学(北京) | Pretreatment method, membrane separation method and system for high-sulfur-content gas |
| CN105169893A (en) * | 2015-07-20 | 2015-12-23 | 合肥科启环保科技有限公司 | Tail gas treatment system |
| CN105543065A (en) * | 2014-12-30 | 2016-05-04 | 浙江大学 | Device for producing biological hydrogen-methane gas for vehicles by urban/rural organic waste fermentation and purification |
| CN105617830A (en) * | 2014-12-30 | 2016-06-01 | 浙江大学 | Method for producing automotive biological hydrogen-alkane gas from urban and rural organic waste through fermentation and purification as well as refinement |
| CN106422773A (en) * | 2016-11-30 | 2017-02-22 | 唐山绿源环保科技有限公司 | Gas hydrogen sulfide removal system and desulfurizing method thereof |
| CN109929636A (en) * | 2017-12-19 | 2019-06-25 | 国家电投集团远达环保工程有限公司重庆科技分公司 | Biogas desulfurization method and device |
| CN110106004A (en) * | 2018-12-29 | 2019-08-09 | 河南农业大学 | Methane desulfurizer, sulfur method and purifying technique |
| CN110747027A (en) * | 2019-10-31 | 2020-02-04 | 广东石油化工学院 | A filter equipment for purification of animal manure methane-generating pit marsh gas |
| CN113660997A (en) * | 2019-04-01 | 2021-11-16 | 三菱动力株式会社 | Device and method for gas purification treatment and/or combustion ash neutralization treatment |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3939204B2 (en) * | 2002-06-12 | 2007-07-04 | 中外炉工業株式会社 | Separation and recovery of methane from digestion gas of organic waste |
| CN101475859A (en) * | 2009-01-21 | 2009-07-08 | 东莞市康达机电工程有限公司 | Method and apparatus for preparing sulfur-free natural gas from methane |
| CN102000486A (en) * | 2010-10-18 | 2011-04-06 | 武汉凯迪电力股份有限公司 | Method for catching carbon dioxide in flue gas by active sodium carbonate and apparatus thereof |
| CN103013600A (en) * | 2012-11-19 | 2013-04-03 | 河南天冠工业沼气有限公司 | Biogas desulfurization method in series of wet method with dry method |
| CN202898377U (en) * | 2012-11-13 | 2013-04-24 | 江苏恒创科技有限公司 | Device for methane decarburization and synchronous preparation of nanometer calcium carbonate |
| CN202924978U (en) * | 2012-11-29 | 2013-05-08 | 孟祥坤 | Methane purifying and generation control device |
| CN103113947A (en) * | 2013-03-06 | 2013-05-22 | 清华大学 | Methane separation and purification device and method thereof for purifying methane by absorbing CO2 through alkaline method |
| CN203960157U (en) * | 2014-05-29 | 2014-11-26 | 湖南和道资源科技有限公司 | A kind of marsh gas treating system |
-
2014
- 2014-05-29 CN CN201410234310.XA patent/CN103980971A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3939204B2 (en) * | 2002-06-12 | 2007-07-04 | 中外炉工業株式会社 | Separation and recovery of methane from digestion gas of organic waste |
| CN101475859A (en) * | 2009-01-21 | 2009-07-08 | 东莞市康达机电工程有限公司 | Method and apparatus for preparing sulfur-free natural gas from methane |
| CN102000486A (en) * | 2010-10-18 | 2011-04-06 | 武汉凯迪电力股份有限公司 | Method for catching carbon dioxide in flue gas by active sodium carbonate and apparatus thereof |
| CN202898377U (en) * | 2012-11-13 | 2013-04-24 | 江苏恒创科技有限公司 | Device for methane decarburization and synchronous preparation of nanometer calcium carbonate |
| CN103013600A (en) * | 2012-11-19 | 2013-04-03 | 河南天冠工业沼气有限公司 | Biogas desulfurization method in series of wet method with dry method |
| CN202924978U (en) * | 2012-11-29 | 2013-05-08 | 孟祥坤 | Methane purifying and generation control device |
| CN103113947A (en) * | 2013-03-06 | 2013-05-22 | 清华大学 | Methane separation and purification device and method thereof for purifying methane by absorbing CO2 through alkaline method |
| CN203960157U (en) * | 2014-05-29 | 2014-11-26 | 湖南和道资源科技有限公司 | A kind of marsh gas treating system |
Non-Patent Citations (1)
| Title |
|---|
| 张学铭等: "《化学小词典》", 31 August 1994, article "化学小词典", pages: 82 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479777A (en) * | 2014-11-20 | 2015-04-01 | 中国石油大学(北京) | Pretreatment method, membrane separation method and system for high-sulfur-content gas |
| CN105543065A (en) * | 2014-12-30 | 2016-05-04 | 浙江大学 | Device for producing biological hydrogen-methane gas for vehicles by urban/rural organic waste fermentation and purification |
| CN105617830A (en) * | 2014-12-30 | 2016-06-01 | 浙江大学 | Method for producing automotive biological hydrogen-alkane gas from urban and rural organic waste through fermentation and purification as well as refinement |
| CN105617830B (en) * | 2014-12-30 | 2018-05-25 | 浙江大学 | The method that town and country fermentation of organic wastes purification produces automobile-used biological hydrogen alkane gas |
| CN105169893A (en) * | 2015-07-20 | 2015-12-23 | 合肥科启环保科技有限公司 | Tail gas treatment system |
| CN106422773A (en) * | 2016-11-30 | 2017-02-22 | 唐山绿源环保科技有限公司 | Gas hydrogen sulfide removal system and desulfurizing method thereof |
| CN109929636A (en) * | 2017-12-19 | 2019-06-25 | 国家电投集团远达环保工程有限公司重庆科技分公司 | Biogas desulfurization method and device |
| CN109929636B (en) * | 2017-12-19 | 2021-08-17 | 国家电投集团远达环保工程有限公司重庆科技分公司 | Biogas desulfurization method and device |
| CN110106004A (en) * | 2018-12-29 | 2019-08-09 | 河南农业大学 | Methane desulfurizer, sulfur method and purifying technique |
| CN113660997A (en) * | 2019-04-01 | 2021-11-16 | 三菱动力株式会社 | Device and method for gas purification treatment and/or combustion ash neutralization treatment |
| CN110747027A (en) * | 2019-10-31 | 2020-02-04 | 广东石油化工学院 | A filter equipment for purification of animal manure methane-generating pit marsh gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103980971A (en) | Methane treatment method and methane treatment system | |
| CN102816619B (en) | Method and device for recovery coupling of biological sulfur and carbon dioxide for producing biogas | |
| CN203342628U (en) | Container-type methane purification membrane method purification system | |
| CN102559316B (en) | Methane purifying method and equipment thereof | |
| CN205627588U (en) | Device of little biological desulfuration of closed circulation and recovery elemental sulfur | |
| CN103254957B (en) | Device and method for removing hydrogen sulfide out of methane by utilizing collagenous fiber/polyester composite material to load Fe(III) | |
| CN103421566B (en) | A kind of natural gas deviates from sulfur recovery technology and device | |
| CN107537293A (en) | A kind of closed cycle bacterial desulfurization and the method for reclaiming elemental sulfur | |
| CN204224559U (en) | A kind of sledge-borne type microbial desulfurization and sulfur recovery facility | |
| CN203960157U (en) | A kind of marsh gas treating system | |
| CN203728792U (en) | High-purity methane purification device | |
| CN102631837B (en) | Integrated type sulfur-containing waste gas purifying device | |
| CN103031172A (en) | Layered biological-chemical combined biogas desulfurizing device | |
| CN105344214A (en) | Liquid-state catalyst flue gas purification integration system and liquid-state catalyst flue gas purification integration process | |
| CN105817129A (en) | Device and method for removing hydrogen sulfide in marsh gas with microorganisms | |
| CN109722317B (en) | CO regeneration based on wet method2Natural gas decarbonization system and method for adsorbing material | |
| CN106497620B (en) | Biogas purification and biogas slurry treatment system and method with biogas slurry as CO2 absorbent | |
| CN107970759B (en) | Adsorbing and recovering CO in high-sulfur-content flue gas2Method (2) | |
| CN1304088C (en) | Apparatus and process for separating carbon dioxide by coal replacement combustion based on calcium sulfate | |
| CN217149105U (en) | Biogas purification system | |
| CN109908717A (en) | Gas circulating type biology bubble tower biogas/natural gas biological desulfurization method | |
| CN206215025U (en) | Desulfurizer containing diversified forms sulfide gaseous mixture | |
| CN108079767B (en) | Adsorbing and recovering CO in high-sulfur-content flue gas2In a device | |
| CN203021521U (en) | Layered biological-chemical combined biogas desulfurization device | |
| CN203694875U (en) | Radial cross-flow moving-bed reactor for removal of hydrogen sulfide by temperature swing adsorption |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: HE SHAOJUN Free format text: FORMER OWNER: HUNAN HARMONY RESOURCE TECHNOLOGY CO., LTD. Effective date: 20150518 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20150518 Address after: 412000 No. 18, No. 26, Zhujiang South Road, Tianyuan District, Hunan, Zhuzhou, 403 Applicant after: He Shaojun Address before: Nine, No. 1986 Zhuzhou Road, Taishan West Road, Tianyuan District, Hunan 412007, China Applicant before: Hunan He Dao resource Science and Technology Ltd. |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140813 |